Rigid-Strut-Containing crown ethers and [2]catenanes for incorporation into Metal-Organic frameworks

DOI: 10.1002/chem.200902350

Rigid-Strut-Containing Crown Ethers and [2]Catenanes for Incorporation

into Metal–Organic Frameworks

Yan-Li Zhao,^[b]Lihua Liu,^[a]Wenyu Zhang,^[b]Chi-Hau Sue,^[a]Qiaowei Li,^[b]

[b, c]

Omar M. Yaghi,^[b]and J. Fraser Stoddart*^[a]

ˇ

Ognjen S. Miljanic´,

Abstract: To introduce crown ethers

into the struts of metal–organic frame-

works (MOFs), general approaches

have been developed for the syntheses

of dicarboxylic acid dibenzo[30]crown-

10 (DB30C10DA), dicarboxylic acid di-

2,3-naphtho[30]crown-10

Vis, fluorescence, and NMR spectro-

scopic techniques. The crystal super-

structure of the complex DMBP·2PF₆ꢀ

BPP34C10DA was determined by X-

[2]catenane

H₂BPP34C10DC-

CAT·4PF₆was investigated by X-ray

crystallography, which revealed race-

mic R and S isomers with planar chiral-

ity present in the crystal in a 1:1 ratio.

These crown ether based struts serve as

excellent organic ligands to bind with

transition metal ions in the construc-

tion of MOFs: the crown ethers

BPP34C10DA and NPP36C10DA in

ray

crystallography.

The

NPP36C10DA-based

[2]catenane

(H₂NPP36C10DC-CAT·4PF₆) and the

BPP34C10DA-based [2]catenane

(H₂BPP34C10DC-CAT·4PF₆) were

prepared in DMF at room temperature

by the template-directed clipping reac-

(DN30C10DA), dicarboxylic acid bis-

paraphenylene[34]crown-10

(BPP34C10DA), and dicarboxylic acid

1,5-naphthoparaphenylene[36]crown-10

(NPP36C10DA). These novel crown

ethers not only retain the characteris-

tics of their parent crown ethers since

they can 1) bind cationic guests and

2) serve as templates for making me-

the presence of ZnACTHUNTRGNE(UNG NO₃)₂·4H₂O af-

tions

of

the

planarly

chiral

forded the MOF-1001 and MOF-1002

frameworks, respectively. The crystal

structures of MOF-1001 and MOF-

NPP36C10DA and BPP34C10DA with

1,1’-[1,4-phenylenebis(methylene)]di-

¯

4,4’-bipyridin-1-ium

bis(hexafluoro-

1002 are both cubic and display Fm3m

phosphate) and 1,4-bis(bromomethyl)-

benzene, respectively. The crystal struc-

symmetry. The unit cell parameter of

the metal–organic frameworks is a=

52.9345 ꢀ. Since such MOFs, contain-

ing electron-donating crown ethers are

capable of docking incoming electron-

accepting substrates in a stereoelec-

tronically controlled fashion, the pres-

ent work opens a new access to the

preparation and application of MOFs.

chanically

interlocked

molecules

(MIMs), such as catenanes and rotax-

anes, but they also present coordina-

tion sites to connect with secondary

building units (SBUs) in MOFs. The

binding behavior of BPP34C10DA with

ture

of

the

dimethyl

ester

the

(BPP34C10DE-CAT·4PF₆)

of

Keywords: catenanes

·

crown

ethers · macrocyclic ligands · metal–

1,1’-dimethyl-4,4’-bipyridinium

bis-

organic frameworks

structures

· solid-state

G

ACHTUNGTRENNUNG

has been investigated by means of UV/

Introduction

[a] Dr. L. Liu, C.-H. Sue, Prof. J. F. Stoddart

Department of Chemistry, Northwestern University

2145 Sheridan Road, Evanston, Illinois 60208 (USA)

Fax : (+1)847-491-1009

E-mail: stoddart@northwestern.edu

Since the so-called crown ethers were discovered by Peder-

sen in 1967,^[1]they have led to a wide variety of applications

in supramolecular chemistry, materials science, nanoscience,

and so on.^[2]One of the most significant properties for

crown ethers is that they can serve as hosts for binding inor-

ganic and organic guests, especially cationic ones.^[1a]On ac-

count of this important property, particular crown ethers

have been employed as templates in the construction of me-

chanically interlocked molecules (MIMs), such as catenanes

and rotaxanes.^[3,4]To expand the collection of functional ma-

terials that can be applied to address some of the technolog-

ˇ

´

[b] Dr. Y.-L. Zhao, W. Zhang, Q. Li, Prof. O. S. Miljanic,

Prof. O. M. Yaghi

Department of Chemistry and Biochemistry

University of California, Los Angeles

607 Charles E. Young Drive East, Los Angeles

California 90095 (USA)

ˇ

´

[c] Prof. O. S. Miljanic

Present address: Department of Chemistry

University of Houston, 136 Fleming Building

Houston, Texas 77204 (USA)

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ical needs of todayꢂs society, such as those of stimuli-respon-

sive materials, drug delivery systems, gas-storage materials,

or sensors for environmental monitoring, medical diagnos-

tics, and gene-chip technologies, the preparation of novel

crown ethers have been highly sought after in recent years.

The relatively difficult preparation and modification of

crown ethers, however, limit their applications. Thus, it is

currently desirable to develop general synthetic approaches

for the preparation and modification of functioning crown

ethers.

ethers, successful and unsuccessful synthetic approaches car-

ried out by us are described and discussed. Crown ethers

and [2]catenanes carrying two carboxylic acid units can

serve as organic ligands to coordinate with secondary build-

ing units (SBUs) for the preparations of metal–organic

frameworks (MOFs).^[10]The crown ethers BPP34C10DA

and NPP36C10DA in the presence of ZnACHTUNGTRNEUNG(NO₃)₂·4H₂O have

afforded^[11]MOF-1001 and MOF-1002 frameworks, respec-

tively. The crystal structures of MOF-1001 and MOF-1002

provide direct evidence for the formation of extended

frameworks. The advantages of these crown ethers in the

preparations of MOFs are that 1) the crown ethers with an

approximately 2 nm strut length—the distance between the

two carbon atoms of the terminal carboxyl groups—are ex-

pected to be employed in the synthesis of MOFs with extra

large pores, 2) the uncomplexed crown ethers in the MOFs

can bind certain guest molecules, and 3) this synthetic strat-

egy may lead to new properties for MOFs, for example, chir-

ality, provided that the appropriate crown ether derivatives

can be resolved.

Crown ethers are flexible compounds,^[2a]a situation that

may result in many possible conformations when they ex-

press their binding properties. To decrease conformational

space, aromatic residues have been introduced into their

constitutions to impart increased rigidity.^[5]Since the

[n]crown-10 analogues, namely, bisparaphenylene[34]crown-

10 (BPP34C10),^[6]1,5-naphthoparaphenylene-[36]crown-10

(NPP36C10),^[7]dibenzo[30]crown-10 (DB30C10),^[8]and di-

2,3-naphtho[30]-crown-10 (DN30C10),^[8]are good macrocy-

clic polyethers for the construction of MIMs by templation,

we herein describe the general syntheses of relatively rigid

aromatic crown ethers, namely, dicarboxylic acid DB30C10

(DB30C10DA), dicarboxylic acid DN30C10 (DN30C10DA),

dicarboxylic acid NPP36C10 (NPP36C10DA), and dicarbox-

ylic acid BPP34C10 (BPP34C10DA), and the preparation

and characterization of the NPP36C10DA-based [2]catenane

(H₂NPP36C10DC-CAT·4PF₆), the BPP34C10DA-based

[2]catenane (H₂BPP34C10DC-CAT·4PF₆), the dimethyl

ester (BPP34C10DE-CAT·4PF₆) of the [2]catenane

Results and Discussion

Synthesis: In this section, we describe in detail the synthetic

procedures employed in the preparation of the target crown

ethers and [2]catenanes. An important starting material,

methyl 4-ethynylbenzoate (2), was prepared by two ap-

proaches (see I and II in Scheme 1) from methyl 4-iodoben-

zoate and ethyl 4-bromobenzoate, respectively. In route I,

compound 2 was prepared from 1 in a yield of 95% accord-

ing to a similar procedure in literature.^[12]In route II, ethyl

4-trimethylsilyl-ethynylbenzoate (3) was formed by reacting

ethyl 4-bromobenzoate and (trimethylsilyl)acetylene in a

yield of 94%. Compound 2 was obtained from 3 in MeOH

with a yield of 99% by desilylation and transesterification

from ethyl benzoate to methyl benzoate. Both these routes

are efficient for the preparation of 2.

H₂BPP34C10DC-CAT·4PF₆,

and

the

complex

(DMBP·2PF₆ꢀBPP34C10DA) of BPP34C10DA with 1,1’-di-

methyl-4,4’-bipyridinium bis(hexafluorophosphate) (DMBP·

2PF₆). Sonogashira couplings^[9]are general approaches de-

veloped in this research toward the synthesis of the dicar-

boxylic acid terminated rigid struts. To establish the best

synthetic approaches for the preparation of these crown

Abstract in Chinese:

As the control compounds for the linearly rigid-strut-con-

taining crown ethers, the struts 8 and 14 were prepared by

using the approaches outlined in Schemes 2 and 3, respec-

tively. 1,4-Diethynyl-2,5-dimethoxybenzene (6) and 1,4-di-

ethynyl-2,3-bis(methoxymethoxy)naphthalene (12) were

prepared from 1,4-diiodo-2,5-dimethoxybenzene (4) and 1,4-

dibromo-2,3-bis(methoxymethoxy)naphthalene (10), respec-

tively, through coupling reactions with (trimethylsilyl)acety-

lene and subsequent desilylation procedures. Precursors 6

and 12 were further treated with methyl 4-iodobenzoate to

afford the strut-containing diACTHNUGRTNEUNG(methyl benzoate)s 7 and 13,

and finally, the struts 8 and 14 were obtained by de-esterifi-

cation of 7 and 13 in yields of 98 and 95%, respectively.

The crown ether DB30C10DA was synthesized by using

two different approaches, as outlined in Schemes 4 and 5. In

the approach outlined in Scheme 4, 1,4-bis(trimethylsilyl)-

2,3-dimethoxybenzene (16) was prepared from 1,2-dime-

thoxybenzene (veratrol) in two steps. Compound 16 was

treated with ICl in CH₂Cl₂to afford 1,4-diiodo-2,3-dime-

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Rigid-Strut-Containing Crown Ethers and Catenanes

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benzene (19). The two meth-

oxymethyl groups in the strut

20, which was prepared by

means of a coupling reaction of

19 with 2, were removed to give

the strut 21. DB30C10DE was

synthesized by the macrocycli-

zation of the strut 21 with the

ditosylate 23. The crown ether

DB30C10DA was then obtained

by de-esterification and subse-

Scheme 1. The preparation of methyl 4-ethynylbenzoate (2). TMS=trimethylsilyl.

quent

acidification

of

DB30C10DE in a total yield of

91%.

thoxybenzene (17). Since the two methyl groups in 17 are

not good leaving groups, we replaced them by methoxy-

methyl groups to afford 1,4-diiodo-2,3-bis(methoxymethoxy)-

Since the yield of the macrocyclization for the preparation

of DB30C10DE is relatively low (16%), we synthesized this

crown ether by an improved approach (Scheme 5). In this

Scheme 2. The preparation of the strut 8.

Scheme 3. The preparation of the strut 14.

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Scheme 4. The preparation of DB30C10DA. TMEDA=tetramethylethylenediamine.

approach, the precursor crown ether 24 was prepared

through the macrocyclization of the ditosylate 23 with the

diol 18 in a higher yield of 34%. After a coupling reaction

between 24 and 2 was carried out, DB30C10DE can be iso-

lated in a yield of 89%. Thus, the approach outlined in

Scheme 5 is a preferable procedure for the preparation of

DB30C10DA.

In analogy with the preparation of DB30C10DA, the

crown ether DN30C10DA was also synthesized using the

two approaches outlined in Schemes 6 and 7. In the ap-

proach outlined in Scheme 6, the crown ether DN30C10DE

was synthesized by macrocyclization between the strut 25

and the ditosylate 27. DN30C10DA can be obtained in a

total yield of 84% by de-esterification and subsequent

acidification of DN30C10DE. The approach outlined in

Scheme 7 affords a better approach for the preparation of

DN30C10DA. The precursor crown ether 28 was prepared

through macrocyclization between the ditosylate 27 and the

diol 9 in a higher yield of 39%. A coupling reaction be-

tween 28 and 2 was then carried out to give the crown ether

DN30C10DE with a yield of 72%. DN30C10DA was finally

prepared from DN30C10DE by using the same procedure

as that described above.

The crown ether NPP36C10DA was synthesized by using

the procedure shown in Scheme 8. The strut 30 carrying two

tetraethyleneglycol chains on its central hydroquinone ring

was prepared by a coupling reaction of 29 with 2. The crown

ether NPP36C10DE was then synthesized by the macrocycli-

zation between the ditosylate 31 and 1,5-dihydroxynaphtha-

lene in a yield of 20%. Thus, NPP36C10DA was obtained

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Rigid-Strut-Containing Crown Ethers and Catenanes

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Scheme 5. The preparation of DB30C10DA.

by de-esterification and subsequent acidification of

NPP36C10DE in a total yield of 96%.

coupling reactions. After the deprotection of the THP units

in 39, the resulting strut 40 was treated with the ditosylate

33 to give the crown ether BPP34C10DE in a relatively low

yield of 10%. In a similar approach (Scheme 13), we carried

out a deprotection to obtain the strut 40 from 7. Since the

strut 40 could not be isolated from its byproducts, the at-

tempted preparation for the crown ether BPP34C10DA fol-

lowing the approach outlined in Scheme 13 failed. Thus, the

approach detailed in Scheme 10 is the preferable procedure

for the preparation of BPP34C10DA.

We employed five different approaches (Schemes 9–13),

including some approaches similar to those employed in the

syntheses of the crown ethers DB30C10DA, DN30C10DA,

and NPP36C10DA, to prepare the crown ether

BPP34C10DA. The approaches outlined in Schemes 9 and

10 for the preparation of BPP34C10DA are similar to that

given in Schemes 5 and 7 used in the preparation of

DB30C10DA and DN30C10DA, namely, macrocyclization

between 33 and 2,5-dibromohydroquinone (or 2,5-diiodohy-

droquinone) was carried out to afford the precursor crown

ether 34 (or 35). After a coupling reaction between 34 (or

35) and 2, BPP34C10DE can be isolated. BPP34C10DA was

obtained finally by de-esterification and subsequent acidifi-

cation of BPP34C10DE in a yield of 94%. Overall, the ap-

proach outlined in Scheme 10 affords a more efficient route

for the preparation of BPP34C10DA than that detailed in

Scheme 9.

The procedure for the preparation of BPP34C10DA

shown in Scheme 11 is similar to the one employed in the

preparation of NPP36C10DA (Scheme 8). The crown ether

BPP34C10DE was synthesized by the macrocyclization be-

tween the ditosylate 31 and hydroquinone in a yield of

24%. BPP34C10DA was then prepared from the crown

ether BPP34C10DE according to the procedure described

above.

The

[2]catenanes

H₂NPP36C10DC-CAT·4PF₆,

BPP34C10DE-CAT·4PF₆, and H₂BPP34C10DC-CAT·4PF₆

were prepared (Scheme 14) by the crown ethers

NPP36C10DA, BPP34C10DE, and BPP34C10DA to tem-

plate the formation of the mechanized interlocked cyclo-

phanes from 1,1’-[1,4-phenylenebis(methylene)]di-4,4’-bipyr-

idin-1-ium bis(hexafluorophosphate) and 1,4-bis(bromome-

thyl)benzene in DMF at room temperature. Following the

reactions, the crude mixtures were purified by column chro-

matography on silica gel (MeOH/NH₄Cl (2m)/MeNO₂=

7:2:1) to afford the corresponding [2]catenanes in yields of

approximately

50%.

The

complex

DMBP·2PF₆ꢀ

BPP34C10DA was prepared from BPP34C10DA and

DMBP·2PF₆in a mixture of Me₂CO and n-pentane at room

temperature. When the solution was left at room tempera-

ture for three days, red block-shape crystals were obtained

and were subjected to X-ray crystallographic analyses.

Scheme 12 summarizes another procedure we have em-

ployed in the preparation of BPP34C10DA. The tetrahydro-

pyranyl (THP)-protected 2,5-dibromohydroquinone 36 was

transformed to the strut 39 in three steps with a series of

A promising application of the linear strut-containing

crown ethers is the construction of MOFs. The crown ethers

BPP34C10DA and NPP36C10DA coordinated by Zn₄O

clusters in MeNH₂/DMF at 658C afforded MOF-1001 and

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Scheme 6. The preparation of DN30C10DA.

MOF-1002, respectively. After the mixture solutions had

cooled to room temperature slowly and naturally, light-

yellow cubic crystals of MOF-1001 and MOF-1002 were col-

lected for X-ray crystallographic analyses.

DMBP·2PF₆, the results indicate that the DMBP·2PF₆guest

is included inside the cavity of the BPP34C10DA macrocy-

cle, leading to significant charge-transfer interactions be-

tween them. The binding constant (K_a) between

BPP34C10DA and DMBP·2PF₆in Me₂CO was obtained by

means of spectrophotometric titration. A value of (829Æ

71)m^À1was obtained.

UV/Vis, fluorescence, and NMR spectroscopies: Since the

crown ethers DB30C10DA, DN30C10DA, NPP36C10DA,

and BPP34C10DA contain linearly conjugated struts, they

showed significant fluorescent properties. It is well known

that DMBP·2PF₆and its derivatives are excellent dicationic

guests for the 30-, 34-, and 36-membered crown ethers.^[6,13]

Thus, we employed BPP34C10DA and DMBP·2PF₆as a

model pair to investigate their binding behavior using UV/

Vis and fluorescence spectrophotometers at room tempera-

ture. The Me₂CO solution of BPP34C10DA turns to red

after the addition of equimolar DMBP·2PF₆. In the UV/Vis

spectra, BPP34C10DA shows (0.50 mm) a maximum absorp-

tion around 377 nm in Me₂CO and the absorption band be-

tween 430–540 nm increases after the addition of the

DMBP·2PF₆guest. In the fluorescence spectra, the maxi-

mum fluorescence intensity (l=458 nm) of BPP34C10DA is

quenched completely upon the addition of equimolar

The inclusion complexation formation of BPP34C10DA

1

and DMBP·2PF₆was evaluated further by means of H, ¹³C,

1

¹⁵N, H–¹H COSY, and H–¹³C HMQC NMR spectroscopies.

To improve the signal-to-noise ratio, isotope-enriched

DMBP·2PF₆with 25% abundance of ¹⁵N was synthesized

and employed in all of the NMR experiments. The protons

in the complex were assigned fully by ¹H–¹H COSY and

¹H–¹³C HMQC NMR experiments. In particular, the

¹H–¹³C HMQC NMR spectrum (Figure 1) of DMBP·2PF₆

(1.2ꢃ10^À3m) and BPP34C10DA (4.0ꢃ10^À4m) shows the

clear correlations between the protons and the related

carbon nuclei in complexed and uncomplexed DMBP·2PF₆

(a, b, and methyl nuclei in the blue lines) and

BPP34C10DA (a and b nuclei of the 4-carboxyphenylethyn-

yl moieties in the black lines and Q1 and Q2 nuclei of the

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Rigid-Strut-Containing Crown Ethers and Catenanes

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Scheme 7. The preparation of DN30C10DA.

hydroquinone moieties in the red lines) in CD₃COCD₃at

200 K. In the H NMR spectra, the a, b, and methyl protons

DMBP·2PF₆. Upon increasing the temperature to 298 K,

these broad peaks coalesce into one peak. The protons in

the crown ether BPP34C10DA show no obvious separation

of the signals under the same conditions.

1

of the DMBP·2PF₆guest shift upfield 0.20, 0.34, and

0.38 ppm (Table 1), respectively, upon complexation with

BPP34C10DA in CD₃COCD₃at 200 K, as a consequence of

the shielding effect of the crown ether. The corresponding

a, b, and methyl carbon nuclei shift upfield 0.5, 2.2, and

0.4 ppm (Table 1) under the same conditions, respectively.

In the ¹⁵N NMR spectra, the uncomplexed DMBP·2PF₆re-

veals a ¹⁵N signal centered at d=206.9 ppm, and the signal

shifts upfield to d=205.2 ppm (Dd=À1.7 ppm) after com-

plexation with BPP34C10DA. These NMR spectroscopic in-

vestigations confirm that the crown ether BPP34C10DA is

capable of binding the DMBP²⁺dication, forming a host–

guest complex.

The protons in the [2]catenanes H₂NPP36C10DC-

CAT·4PF₆, BPP34C10DE-CAT·4PF₆, and H₂BPP34C10DC-

1

CAT·4PF₆were assigned fully by H–¹H COSY experiments

1

at 298 K. The VT H NMR experiments on the [2]catenanes

were conducted to investigate the dynamics of the [2]cate-

nanes, namely, the pirouetting of the cyclobis(paraquat-p-

phenylene) (CBPQT⁴⁺) rings around the macrocycles. Since

H₂BPP34C10DC-CAT·4PF₆exhibits poor solubility, we em-

ployed its analogue, BPP34C10DE-CAT·4PF₆, to perform

the VT NMR experiments in CD₃COCD₃. Partial VT

¹H NMR spectra of BPP34C10DE-CAT·4PF₆are shown in

Figure 3 and the kinetic and thermodynamic parameters for

the dynamic process observed in BPP34C10DE-CAT·4PF₆

The signal splits of the a, b, and methyl protons in

DMBP·2PF₆upon complexation with BPP34C10DA were

only observed at low temperatures, when the exchange of

the complexed and uncomplexed DMBP·2PF₆was slowed

down on the NMR timescale. To investigate the dynamic be-

havior of the complex DMBP·2PF₆ꢀBPP34C10DA, varia-

1

are listed in Table 2. In the H NMR spectrum at 245 K, the

a, b, and CH₂protons on the CBPQT⁴⁺ring show mainly

two, two, and three broad peaks, respectively. With increas-

ing the temperature to 295 K, these broad peaks coalesce

1

ble-temperature (VT) H NMR experiments of DMBP·2PF₆

into one peak. These spectral changes correspond to the

(1.2ꢃ10^À3m) with BPP34C10DA (4.0ꢃ10^À4m) were carried

out in CD₃COCD₃. Typically, the a, b, and methyl protons

of DMBP·2PF₆in the NMR spectra (Figure 2) at 217 K fea-

ture two broad peaks, respectively, which are assigned to the

proton signal of the complexed and uncomplexed

free energy of activations (DG_c^°

)

of 10.6 (a protons), 10.6

[14]

(b protons), and 10.5 (CH₂protons) kcalmol^À1. The free

energy values are found to be lower than that (12.0 kcal

mol^À1) observed previously^[15]for other CBPQT⁴⁺ring-

based [2]catenane systems, probably because the introduc-

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Scheme 8. The preparation of NPP36C10DA. DMAP=4-dimethylaminopyridine, Ts=p-toluenesulfonyl.

Scheme 9. The preparation of BPP34C10DA.

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Rigid-Strut-Containing Crown Ethers and Catenanes

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Scheme 10. The preparation of BPP34C10DA.

Scheme 11. The preparation of BPP34C10DA.

tion of the linearly rigid struts to the crown ethers limits ef-

ficient pirouetting of the CBPQT⁴⁺ring in the [2]catenanes.

crystal data and experimental and refinement parameters

for these crystals are listed in Table 3. Single-crystal 31, an

important precursor for the rigid-strut-containing crown

ethers, is monoclinic and has a space group of P21/c. In its

crystal structure (Figure 4), two terminal phenylene rings in

the methyl benzoate units are twisted with respect to the

central hydroquinone ring (338 of dihedral angles between

the terminal phenylene rings and the central hydroquinone

Crystal structures and geometrical analyses: Direct evidence

for the formation of good quality single crystals for 31,

BPP34C10DE,

NPP36C10DA,

DMBP·2PF₆ꢀ

BPP34C10DA,^[11]BPP34C10DE-CAT·4PF₆, MOF-1001,^[11]

and MOF-1002^[11]has been obtained in the solid state. The

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J. F. Stoddart et al.

Scheme 12. The preparation of BPP34C10DA. PPTS=pyridinium p-toluenesulfonate.

Scheme 13. The preparation of BPP34C10DA.

ring) on the fully rigid conjugated framework. Each of the

tosylated diethyleneglycol chains in 31 adopts an S-shaped

geometry. The packing structure of the compound 31 is sta-

bilized by intermolecular p–p stacking interactions and hy-

drogen bonds between the oxygen atoms of the tetraethyl-

eneglycol chains and the protons of the tosyl benzene rings

in neighboring molecules, between the oxygen atoms of the

sulfonyl groups and the protons of the tetraethyleneglycol

chains in neighboring molecules, and between the oxygen

atoms of the tetraethyleneglycol chains and the methyl pro-

tons of the methyl benzoate units in neighboring molecules.

The crystal structure of the crown ether BPP34C10DE is

¯

triclinic and has (Table 3) a space group of P1. In common

with 31, two terminal phenylene rings in the methyl ben-

zoate units are twisted with respect to the central hydroqui-

none ring (16 and 198 of dihedral angles between the termi-

13366

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Chem. Eur. J. 2009, 15, 13356 – 13380

Rigid-Strut-Containing Crown Ethers and Catenanes

FULL PAPER

Scheme 14. The syntheses of H₂NPP36C10DC-CAT·4PF₆, BPP34C10DE-CAT·4PF₆, and H₂BPP34C10DC-CAT·4PF₆.

nal phenylene rings and the central hydroquinone ring, re-

spectively) in the crystal structure of BPP34C10DE

(Figure 5). The two hydroquinone rings in the crown ether

are not parallel; they have a dihedral angle of 1258. The two

hydroquinone rings have anti geometries associated with the

conformation of the tetraethyleneglycol chains. The packing

structure of the crystal BPP34C10DE may be stabilized by

intermolecular hydrogen bonds between the oxygen and hy-

drogen atoms in the tetraethyleneglycol chains. The fact of

the matter is that the rigid-strut-containing crown ethers

BPP34C10DA,

BPP34C10DE,

NPP36C10DA,

and

NPP36C10DE have planar chirality, since they have no

planes or centers of symmetry.^[16]The planar chirality of the

crown ethers can be demonstrated by their crystal struc-

tures. We note that both racemic R and S enantiomers are

present in

a 1:1 ratio in the crystal structure of

BPP34C10DE (Figure 5).

The crystal structure of the crown ether NPP36C10DA is

triclinic and has a space group of P1 (Table 3). Two terminal

phenylene rings in the benzoic acid units are twisted with re-

¯

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13367

J. F. Stoddart et al.

Figure 2. Partial ¹H NMR spectra of DMBP·2PF₆(1.2ꢃ10^À3m) and

BPP34C10DA (4.0ꢃ10^À4m) in CD₃COCD₃at various temperatures. The

exchange of the complexed and uncomplexed DMBP·2PF₆was slowed

down at low temperatures, leading to the splits of the a, b, and methyl

proton signals in DMBP·2PF₆.

Figure 1. Partial ¹H–¹³C HMQC spectrum of DMBP·2PF₆(1.2ꢃ10^À3m)

and BPP34C10DA (4.0ꢃ10^À4m) in CD₃COCD₃at 200 K. The abscissa

shows the ¹H NMR spectrum and the ordinate shows the ¹³C NMR one.

Correlations among nuclei in DMBP·2PF₆(blue lines), and 4-carboxy-

phenylethynyl (black lines) and hydroquinone (red lines) moieties of

BPP34C10DA are indicated in the spectrum. The nuclei in the com-

plexed DMBP·2PF₆label as a, b, and N-Me and these in the uncom-

plexed DMBP·2PF₆label as a_u, b_u, and N-Me_u. The nuclei are defined

alongside their structural formulas.

Table 1. Changes of chemical shifts of selected nuclei in the complex (d_c)

DMBP·2PF₆ꢀBPP34C10DA (1.2ꢃ10^À3m) as compared to those of the

uncomplexed (d_u) DMBP·2PF₆(1.2ꢃ10^À3m) in CD₃COCD₃at 200 K. Dd

is the chemical shift difference.

Nuclei

¹H

¹³C

¹⁵N

a

b

N-Me

a

b

N-Me

d_u[ppm]

d_c[ppm]

Dd [ppm]

9.50

8.96

À0.20

8.96

8.62

À0.34

4.72

4.34

À0.38

147.1

146.6

À0.5

126.7

124.5

À2.2

48.5

48.1

À0.4

206.9

205.2

À1.7

spect to the central hydroquinone ring (16 and 1578 of dihe-

dral angles between the terminal phenylene rings and the

central hydroquinone ring, respectively) in the crystal struc-

ture of NPP36C10DA (Figure 6). The 1,5-dihydroxynaphtha-

lene unit and central hydroquinone ring in the crown ether

are not parallel; they have a dihedral angle of 618. The

packing structure of the crystal NPP36C10DA is stabilized

by intermolecular p–p stacking interactions and hydrogen

bonds between the oxygen atoms of the carboxylic acid

units and the protons of the tetraethyleneglycol chains in

neighboring molecules, between the oxygen atoms of the

tetraethyleneglycol chains and the protons of the central hy-

droquinone ring in neighboring molecules, and between the

carboxylic acid groups in the adjacent molecules.

NPP36C10DA displays its planar chirality with 1:1 racemic

R and S enantiomers in the crystal structure.

Figure 3. Partial VT ¹H NMR spectra of the [2]catenane BPP34C10DE-

CAT·4PF₆in CD₃COCD₃.

Table 2. Kinetic and thermodynamic parameters for the pirouetting pro-

cess of CBPQT⁴⁺resonances in BPP34C10DE-CAT·4PF₆. Dn is the

chemical shift difference between the coalescing signals at low tempera-

ture in the absence of exchange. k_cis calculated from the expression, k_c=

p(Dn)/2^1/2. T_cis the temperature of the spectrometer probe at coales-

cence. The Eyring equation was employed to calculate activation energy

DG_c^°

.

Probe protons

Dn [Hz]

k_c[s^À1

]

T_c[K]

DG_c^°[kcalmol^À1

]

a

42.3

24.5

136.0

92.9

52.8

300.7

251

245

262

10.6

10.5

b

CH₂

The

crystal

superstructure

of

the

complex

DMBP·2PF₆ꢀBPP34C10DA is triclinic and has a space

shows clearly that the p-electron-deficient bipyridinium di-

cation DMBP·2PF₆is inserted through the middle of the

¯

group of P1 (Table 3). The crystal superstructure (Figure 7)

13368

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Chem. Eur. J. 2009, 15, 13356 – 13380

Rigid-Strut-Containing Crown Ethers and Catenanes

FULL PAPER

Table 3. Crystal data, experimental and refinement parameters for the crystals 31, BPP34C10DE, NPP36C10DA, DMBP·2PF₆ꢀBPP34C10DA, and

BPP34C10DE-CAT·4PF₆.

31

BPP34C10DE

NPP36C10DA

DMBP·2PF6ꢀBPP34C10DA

BPP34C10DE-CAT·4PF6

molecular formula

C₅₆H₆₂O₁₈S₂

1087.18

100(2)

C₄₈H₅₂O₁₄

852.90

100(2)

C₅₆H₆₄O₁₅

977.07

100(2)

C_65.5H₇₆F₁₂N₂O_16.5P₂

1446.22

100(2)

C94H101F24N9O15P4

2176.72

100(2)

M_r[gmol^À1

T [K]

]

l [ꢀ]

0.71073

monoclinic

P21/c

8.1408(3)

10.1129(4)

32.1022(14)

90

96.582(3)

90

2625.46

2

1.54178

triclinic

P1

0.71073

triclinic

P1

1.54178

0.71073

monoclinic

P21/n

13.654(3)

29.947(6)

24.499(5)

90

96.253(2)

90

9958(4)

4

1.452

0.188

crystal system

space group

a [ꢀ]

b [ꢀ]

c [ꢀ]

triclinic

¯

P1

9.0342(3)

13.5428(5)

18.2351(6)

81.512(2)

77.525(2)

83.614(2)

2147.22(13)

2

9.52(8)

11.0078(4)

16.9569(6)

19.1579(7)

73.836(2)

83.257(2)

85.681(2)

3407.5(2)

2

13.34(11)

21.27(18)

101.73(7)

98.67(7)

97.67(7)

2576.73

a [8]

b [8]

g [8]

V [ꢀ³]

Z

2

1_calcd[gcm^À3

]

1.375

0.178

1.319

0.802

1.259

0.091

1.409

1.469

m (Mo_Ka) [mm^À1

]

F

(000)

1148

904

1040

1506

4496

crystal size [mm³]

0.41ꢃ0.33ꢃ0.02

2.11–30.56

À11ꢁhꢁ11

À14ꢁkꢁ13

À45ꢁlꢁ45

30395

0.36ꢃ0.17ꢃ0.13

2.50–48.82

À8ꢁhꢁ8

À13ꢁkꢁ12

À16ꢁlꢁ17

8826

0.35ꢃ0.20ꢃ0.10

2.25–32.47

À13ꢁhꢁ11

À18ꢁkꢁ18

À30ꢁlꢁ30

23120

0.10ꢃ0.10ꢃ0.05

2.41–43.99

À9ꢁhꢁ9

À15ꢁkꢁ15

À16ꢁlꢁ17

9915

0.40ꢃ0.20ꢃ0.15

3.79–28.26

À18ꢁhꢁ18

À39ꢁkꢁ39

À32ꢁlꢁ32

87664

q range for data collection [8]

index ranges

no. of reflns collected

no. of unique reflns

R_int

7898

0.2830

3697

0.0226

13940

0.4304

4650

0.0554

24449

0.0708

data/restraints/parameters

goodness-of-fit on F²

R₁(I>2s (I))

7898/0/345

0.815

0.0696

3697/0/561

1.042

0.0348

13940/0/647

0.721

0.0994

4650/65/620

1.061

0.0961

24449/0/1381

1.020

0.0708

wR₂(all data)

0.1610

0.381/À0.419

0.0891

0.198/À0.160

0.2847

0.481/À0.294

0.2525

0.771/À0.447

0.2057

0.785/À0.724

D1 max/min [eꢀ^À3

]

Figure 4. The crystal structure of 31. The hydrogen atoms are omitted for

the sake of clarity. Tetraethyleneglycol chains, tosyl units, and central hy-

droquinone ring are colored red and the rest is colored black.

macrocyclic ring, forming a 1:1 host–guest complex. The two

terminal methylene groups of DMBP·2PF₆protrude above

and below the periphery of the macrocyclic ring, respective-

ly, in a pseudorotaxane-like manner. The interplanar separa-

tion between the bipyridinium ring in DMBP·2PF₆and each

hydroquinone ring is approximately 3.7 ꢀ. This host–guest

geometry is similar to that in the crystal superstructure^[6]of

the 1:1 complex between the crown ether BPP34C10 and

DMBP·2PF₆. The DMBP·2PF₆ꢀBPP34C10DA complex is

stabilized by weak p–p stacking interactions between the bi-

Figure 5. a) Side view of the R isomer and b) side view of the S isomer

for the crystal structure of the crown ether BPP34C10DE. The hydrogen

atoms are omitted for the sake of clarity. Tetraethyleneglycol chain and

hydroquinone rings are colored red and the rest is colored black.

pyridinium ring and the two hydroquinone rings (4 and 118

of dihedral angles between the bipyridinium ring and the

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13369

J. F. Stoddart et al.

AHCTUNGTRENNUNG

The crystal structure of the [2]catenane BPP34C10DE-

CAT·4PF₆is monoclinic and has a space group of P21/n

(Table 3). There are both R and S isomers (Figure 8) with a

1:1 ratio present in the crystal cell, in keeping with the

planar chirality of the [2]catenane. For each isomer, the

crystal structure of the [2]catenane BPP34C10DE-

CAT·4PF₆reveals alternating p-donor/p-acceptor stacking

interactions as a consequence of the threading of the

BPP34C10DE macrocycle through the inside of the

CBPQT⁴⁺ring. One hydroquinone ring is inside and the

other is alongside the CBPQT⁴⁺ring, while one bipyridini-

um unit is inside and the other is alongside the

BPP34C10DE macrocycle. The mean plane separations of

7.1 ꢀ between the two hydroquinone rings in BPP34C10DE

and of 7.1 ꢀ between the two bipyridinium rings equate

with interplanar separations of approximately 3.5 ꢀ between

the p donors and acceptors.^[6]The [2]catenane is stabilized

by weak p–p stacking interactions between the alternating

Figure 6. a) Side view of the R isomer and b) side view of the S isomer

for the crystal structure of the crown ether NPP36C10DA. The hydrogen

atoms are omitted for the sake of clarity. Tetraethyleneglycol chain, 1,5-

dihydroxynaphthalene ring, and central hydroquinone ring are colored

red and the rest is colored black.

À

two hydroquinone rings, respectively), and C H···O hydro-

gen bonds between the oxygen atoms of the tetraethylene-

glycol chains and the a protons of the bipyridinium ring in

DMBP·2PF₆and between the oxygen atoms of the tetra-

À

bipyridinium rings and the hydroquinone rings and C H···O

hydrogen bonds between the oxygen atoms of the tetraeth-

yleneglycol chains and the a protons of the bipyridinium

ring inside the macrocycle and between the oxygen atoms of

the tetraethyleneglycol chains and the methylene protons of

the CBPQT⁴⁺ring. The values for the twist angles (q) and

for other angles (y and f) associated with the bowing of the

aromatic residues in the CBPQT⁴⁺ring are similar to the

values reported^[6]previously for the BPP34C10/CBPQT⁴⁺

[2]catenane. Both the hydroquinone rings have an anti ge-

ometry associated with the conformation of the tetraethyl-

AHCTUNGTREGeNNUN neglycol chains. Two terminal phenylene rings in the

methyl benzoate units are twisted with respect to the central

hydroquinone ring (21 and 128 of dihedral angles between

the terminal phenylene rings and the central hydroquinone

ring, respectively) in the crystal structure. In the packing

structure of the [2]catenane, intermolecular p–p stacking in-

teractions and the hydrogen-bond network associated with

Figure 7. a) Side view of the R isomer and b) top view of the S isomer for

the crystal superstructure of the complex DMBP²⁺ꢀBPP34C10DA. Hy-

drogen atoms, solvent molecules, and counterions are omitted for the

sake of clarity. Tetraethyleneglycol chains and two hydroquinone rings

are colored red, DMBP²⁺is colored blue, and the rest is colored black.

13370

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Chem. Eur. J. 2009, 15, 13356 – 13380

Rigid-Strut-Containing Crown Ethers and Catenanes

FULL PAPER

harvested for unit cell determi-

nation of MOF-1002 from a

total of 240 frames. The

q

range for the unit cell determi-

nation is 2.350–37.3758. The

Bravis lattice of cubic F with

a=52.9482 ꢀ was chosen. In

the crystal structures of the

MOFs, solvent molecules exist

as guests inside the pores. The

crown

BPP34C10DA

ether

struts

and

NPP36C10DA in MOFs present

planar chirality with equal num-

bers of R and S enantiomers,

that is, the extended structures

are racemic with respect to the

planes of chirality generated at

the hyrdoquinone ring, incorpo-

rating both the struts and the

crown ethers. Two carboxylate

groups of the crown ether strut

BPP34C10DA

or

Figure 8. The crystal structure of the [2]catenane BPP34C10DE-CAT⁴⁺: a) side view of the R isomer, b) top

view of the R isomer, c) side view of the S isomer, and d) top view of the S isomer. Hydrogen atoms, solvent

molecules, and counterions are omitted for the sake of clarity. Tetraethyleneglycol chain and two hydroqui-

none rings are colored red, the CBPQT⁴⁺ring is colored blue, and the rest is colored black.

NPP36C10DA were coordinat-

ed with Zn²⁺joints to afford

the cubic structures. In each

cube (Figure 9), eight Zn₄O-

AHCTUNTGREG(NUNN CO₂)₆serve as the joints of the

cube and twelve free macrocy-

the alternating R/S isomers and intervening solvent mole-

cules and counterions extend the [2]catenanes to a higher

architectural level.

The crystals of MOF-1001 and MOF-1002 were prepared

in the oven isothermally. Bulk purities of MOF-1001 and

MOF-1002 were characterized by elemental analysis,

powder X-ray diffraction, and solid-state ¹³C NMR spectros-

copy. The crystals MOF-1001 and MOF-1002 (Figure 9) are

¯

cubic with Fm3m symmetry. The length of an edge (strut

and metal oxide) in MOF-1001 and MOF-1002 cubes is ap-

proximately 26.5 ꢀ, making them the largest in the crystal-

line non-interpenetrating isoreticular MOF series.^[10]Single-

crystal X-ray diffraction investigations indicate that MOF-

1002 shares an identical cubic backbone with MOF-1001, af-

firming the generality of such synthetic methodology for

building a variety of crystalline structures with complexity.

Crystal data for MOF-1001 are C₇₂H₃₆O₁₃Zn₄, M_r=1370.49,

a=52.9345(7) ꢀ, V=148326(3) ꢀ³, 1_calcd=0.123 gcm^À3, l=

1.54178 ꢀ, Z=8, reflections: 57237, independent reflec-

tions: 1508, R₁(I>2s(I))=0.0820, wR₂(all data)=0.2588,

and GOF=1.042. To prove the correctness of the atomic po-

sitions in the framework, the application of the

SQUEEZE^[17]routine of Spek has been performed with the

backbone framework only. If all the atoms in the framework

are considered, the calculated empirical formula is

Figure 9. Space-filling representation of the crystal structures of a) MOF-

1001 and b) MOF-1002. Hydrogen atoms and solvent molecules are omit-

ted for the sake of clarity. Crown ether units with tetraethyleneglycol

chain and two hydroquinone rings are colored red, the rigid struts are

colored black, and the metal joints are colored blue.

C

₁₃₈H₁₃₈O₄₃Zn₄with a density of 0.246 gcm^À3.^[11]Atomic co-

ordinates of MOF-1002 were simulated based on the struc-

ture of MOF-1001.^[11]986 reflections with min. I/s 20 were

Chem. Eur. J. 2009, 15, 13356 – 13380

ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

13371

J. F. Stoddart et al.

tra (HR-MALDI) were obtained on an AppliedBiosystems DE-STR

MALDI time-of-flight mass spectrometer. The reported molecular mass

(m/z) values were the most abundant monoisotopic mass. High-resolution

electrospray ionization (ESI) mass spectra were measured on a Micro-

mass Q-Tof Ultima (SCS, University of Illinois). The X-ray intensity data

collected either on a Bruker SMART APEXII three circle diffractometer

equipped with a CCD area detector and operated at 1200 W power

(40 kV, 30 mA) to generate Cu_Karadiation (l=1.5418 ꢀ) or equipped

with a CCD area detector and operated at 1500 W power (50 kV, 30 mA)

to generate Mo_Karadiation (l=0.71073 ꢀ). The incident X-ray beam was

focused and monochromated by using a Bruker Excalibur Gobel mirror

optic.

cles are anchored in the edges of the cube. Based on the

overall geometries and stoichiometries of the frameworks, it

can be concluded that the rigid-strut-containing crown

ethers can be integrated precisely and periodically into the

robust frameworks of MOFs. Thus, the extended frame-

works provide excellent scaffolding for expressing recogni-

tion sites in three-dimensional space.

Conclusion

Compound 1:^[12]Methyl 4-iodobenzoate (15.7 g, 60.0 mmol), [PdCl₂-

AHCTUNGTRENN(GUN PPh₃)₂] (2.10 g, 2.99 mmol), CuI (0.11 g, 0.58 mmol), iPr₂NH (90 mL),

Sonogashira couplings are central to the general approaches

developed in this research directed toward the synthesis of

dicarboxylic acid terminated rigid struts, incorporating the

aromatic crown ethers DB30C10, DN30C10, BPP34C10,

and NPP36C10, which we have identified as DB30C10DA,

DN30C10DA, BPP34C10DA, and NPP36C10DA prior to

their incorporation into metal–organic frameworks. During

the course of the synthesis of the dicarboxylic acids, we

became aware of the planar chirality associated with the

para-disubstituted hydroquinone rings in BPP34C10DA and

NPP36C10DA. It has not escaped our attention that deriva-

tives of these particular crown ethers, provided the struts

are sufficiently long to prevent their passing through the

middle of the macrocyclic polyethers, could be obtained as

optically active compounds either 1) following their resolu-

tion in bulk quantities by classical methods, or 2) after sepa-

ration of enantiomers on chiral high-performance liquid

chromatography columns, or 3) by carrying out asymmetric

Sonogashira couplings^[9h]to generate the planar prochirality

enantioselectively in the paracyclophane-like crown ether

struts during their synthesis.

The synthetic work described herein establishes that the

necessary strut precursors with symmetrically located crown

ether receptors can be prepared in sufficiently large quanti-

ties, so that they can be employed subsequently in the prep-

aration of metal–organic frameworks containing active do-

mains, namely, recognition sites for particular substrates, for

example, the paraquat dication. There is also every prospect

of being able to prepare homochiral extended structures in

which the source of the handedness in the struts is that of

planar chirality.

and Et₃N (200 mL) were added to a three-necked flask equipped with a

condenser and a magnetic stirrer, and supplied with an inert atmosphere.

The mixture was purged with Ar flow with stirring for 30 min and then

trimethylsilylacetylene (2.78 g, 28.3 mmol) was added. The reaction mix-

ture was slowly heated to 808C and stirred for 8 h at this temperature.

After cooling to room temperature, the reaction mixture was filtered to

remove insoluble materials, and the solid was washed with CH₂Cl₂. The

filtrates were combined and the solvents were removed under reduced

pressure to afford a yellowish orange residue, which was extracted with

CH₂Cl₂(500 mL). The organic layer was washed twice with H₂O and

dried (MgSO₄), before removing the solvent to give compound 4 (13.3 g,

95%) as a yellow powder. It was pure enough to be employed directly in

the next reaction. ¹H NMR (500 MHz, CDCl₃, TMS): d=0.26 (s, 9H),

3.91 (s, 3H), 7.50–7.52 (d, J=8.7 Hz, 2H), 7.95–7.97 ppm (d, J=8.3 Hz,

2H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=0.0, 52.1, 97.6, 104.0, 127.7,

129.3, 129.6, 131.8, 166.4 ppm.

Compound 3:^[18]Ethyl 4-bromobenzoate (2.00 g, 8.73 mmol) was dis-

solved in DMF (80 mL) and iPr₂NH (20 mL). Under Ar protection, tri-

methylsilylacetylene (1.29 g, 13.1 mmol), [PdACHTNURTGNEUNG(PPh₃)₄] (0.50 g, 0.44 mmol),

and CuI (0.04 g, 0.44 mmol) were added to the solution. The mixture was

then stirred under Ar at 808C for 48 h. The solvent was then removed in

vacuo. The residue was dissolved in CH₂Cl₂(50 mL) before being washed

with H₂O (2ꢃ20 mL) and brine (20 mL). The organic phase was then

dried (Na₂SO₄). After the solvent was removed in vacuo, column chroma-

tography (SiO₂: hexane/CH₂Cl₂=3:1) was carried out to provide the

product 3 as a yellow solid (2.03 g, 94%). ¹H NMR (500 MHz, CDCl₃,

TMS): d=0.26 (s, 9H; SiACTHNUTRGNEUNG(CH₃)₃), 1.37–1.40 (t, J=7.1 Hz, 3H; CH₃),

4.36–4.38 (q, J=7.1 Hz, 2H; CH₂), 7.50–7.52 (d, J=8.7 Hz, 2H; Ar-H),

7.76–7.78 ppm (d, J=8.7 Hz, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃,):

d=0.20, 14.7, 61.5, 98.0, 104.5, 128.0, 129.7, 130.4, 132.2, 166.4 ppm;

HRMS (ESI-TOF): m/z calcd for C₁₄H₁₉O₂Si⁺[M+H]⁺: 247.1149; found:

247.1147.

Compound 2:^[12]Compound 1 (0.81 g, 3.49 mmol) was dissolved in a mix-

ture of MeOH (50 mL) and CH₂Cl₂(50 mL), and K₂CO₃(2.42 g,

17.5 mmol) was added. The reaction mixture was purged with Ar flow

for 15 min and stirred at room temperature for 2 h. Most of solvents

were removed under reduced pressure and H₂O (50 mL) was added to

the reaction mixture. The mixture was extracted with Et₂O (2ꢃ50 mL),

and then the combined organic extracts were washed with brine (3ꢃ

50 mL). The combined organic extracts were then dried (Na₂SO₄) and fil-

tered, and the solvent was evaporated in vacuo. Column chromatography

(SiO₂: hexane/CH₂Cl₂=3:1) was carried out to afford the product 2 as a

white solid (0.53 g, 95%). ¹H NMR (500 MHz, CDCl₃, TMS): d=3.23 (s,

Experimental Section

General: All reagents were purchased and used without further purifica-

tion. Thin-layer chromatography (TLC) was performed on glass plates,

precoated with silica gel 60 with fluorescent indicator. The plates were in-

spected by UV light. Column chromatography was carried out on silica

gel 60F. UV/Vis spectroscopy was performed on an Agilent 8453 spectro-

photometer system at 258C. Emission spectra were recorded on a cou-

pled charge device (CCD) through a SpectraPro 2300i 0.300 m imaging

Triple Grating monochromator/spectrograph, excited by a 377 nm/16 mW

laser. NMR spectra were recorded on a Bruker ARX500 (500 MHz),

DRX500 (500 MHz), or AV600 (600 MHz) spectrometer. Chemical shifts

are reported in parts per million (ppm) downfield from the Me₄Si reso-

nance, which was used as the internal standard when recording NMR

spectra. High-resolution matrix-assisted laser desorption/ionization spec-

ꢂ

1H; C CH), 3.92 (s, 3H; OCH₃), 7.53–7.55 (d, J=8.7 Hz, 2H; Ar-H),

7.96–7.99 ppm (d, J=8.7 Hz, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃,

TMS): d=52.1, 79.9, 82.7, 126.6, 129.3, 130.0, 131.9, 166.3 ppm; HRMS

+

(ESI-TOF): m/z calcd for C₁₀H₉O₂[M+H]⁺: 161.0597; found: 161.0590.

Compound

2 was also prepared from 3 as follows: K₂CO₃(0.43 g,

3.04 mmol) was added to a solution of 3 (0.25 g, 1.01 mmol) in MeOH

(10 mL) and the solution was stirred at room temperature for 2 h. The

solid material was removed by filtration and the solvent was removed in

vacuo. The residue was then dissolved in CH₂Cl₂(5 mL) before being

washed with H₂O (2ꢃ3 mL) and brine (3 mL). The organic phase was

then dried (Na₂SO₄). After the solvent was removed in vacuo, column

13372

www.chemeurj.org

ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eur. J. 2009, 15, 13356 – 13380

Rigid-Strut-Containing Crown Ethers and Catenanes

FULL PAPER

chromatography (SiO₂: hexane/CH₂Cl₂=3:1) was carried out to afford

the product 2 as a white solid (0.18 g, 99%).

CDCl₃, TMS): d=6.17 (s, 2H; OH), 7.51–7.53 (d, 2H; Ar-H), 8.07–

8.09 ppm (d, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=107.3,

125.1, 125.8, 128.8, 148.5 ppm; MS (ESI-TRAP): m/z: 315.90 [M]⁺.

Compound 4:^[19]ICl (175 g, 1.08 mol) was added dropwise to MeOH

(300 mL) below 158C. 1,4-Dimethoxybenzene (34.5 g, 0.25 mol) was

added to the mixture below 158C and then the reaction mixture was

heated under reflux for 4 h. After cooling the reaction mixture to room

temperature, the resulting crystals were collected by filtration. The crys-

tals were rinsed with cold MeOH and air dried to give the product 4

(84.0 g, 84%). ¹H NMR (500 MHz, CDCl₃, TMS): d=3.82 (s, 6H;

OCH₃), 7.19 ppm (s, 2H; Ar-H).

Compound 10: A solution of iPr₂NH (12.5 mL, 72.0 mmol) in dry THF

(20 mL) was added slowly to a solution of the compound 9 (9.54 g,

30.0 mmol) in dry THF (100 mL) under an Ar atmosphere. The reaction

mixture was stirred for 30 min at room temperature, and then

ClCH₂OMe (5.80 g, 5.5 mL, 72.0 mmol) was added by syringe. The result-

ing mixture was stirred overnight at room temperature. The insoluble

ammonium salts were filtered off to give a filtrate. After the solvent was

removed in vacuo, column chromatography (SiO₂: hexane/CH₂Cl₂=2:1)

was carried out to afford the product 10 (3.50 g, 86%). ¹H NMR

(500 MHz, CDCl₃, TMS): d=3.69 (s, 6H; OCH₃), 5.38 (s, 4H; OCH₂O),

7.52–7.54 (d, 2H; Ar-H), 8.08–8.10 ppm (d, 2H; Ar-H); ¹³C NMR

(125 MHz, CDCl₃, TMS): d=55.2, 93.8, 103.4, 125.6, 126.1, 129.4,

153.8 ppm; MS (ESI-TRAP): m/z: 403.89 [M]⁺.

Compound 5:^[20]1,4-Diiodo-2,5-dimethoxybenzene 4 (18.0 g, 46.0 mmol),

[PdACHTUNGTRENNUNG(PPh₃)₄] (1.05 g, 0.92 mmol), CuI (0.35 g, 1.84 mmol), and Et₃N

(200 mL) were added to a three-necked flask equipped with a condenser

and a magnetic stirrer under an inert atmosphere. The mixture was

purged with an Ar flow with stirring for 30 min before trimethylsilylace-

tylene (13.9 g, 142 mmol) was added. The reaction mixture was slowly

heated to 808C and stirred for 8 h at this temperature. After cooling to

room temperature, the insoluble material was collected by filtration and

then rinsed with CH₂Cl₂(650 mL). The solution in CH₂Cl₂was combined

with the filtrate and the organic phase was washed with H₂O (2ꢃ

200 mL), and dried (MgSO₄). The solvent was removed in vacuo and the

Compound 11: Compound 10 (12.2 g, 30.0 mmol), [Pd

0.53 mmol), CuI (0.22 g, 1.05 mmol), PPh₃(0.30 g, 1.14 mmol), iPr₂NH

(55 mL), and Et₃N (150 mL) were added to three-necked flask

ACHTUNGTREN(UNNG PPh₃)₄] (0.60 g,

a

equipped with a condenser and a magnetic stirrer under an inert atmos-

phere. The mixture was purged with Ar and stirred for 30 min before tri-

methylsilylacetylene (7.51 g, 76.4 mmol) was added. The reaction mixture

was slowly heated to 808C and stirred for 8 h at this temperature. After

cooling the solution to room temperature, the insoluble material was col-

lected by filtration. The solid was extracted with CH₂Cl₂(450 mL). The

organic layer was washed with H₂O (2ꢃ100 mL) and dried (MgSO₄). The

solvent was removed in vacuo to afford the crude product. Column chro-

matography (SiO₂: hexane/EtOAc=2:1) was carried out to provide 11 as

a light-yellow solid (12.7 g, 98%). ¹H NMR (500 MHz, CD₂Cl₂, TMS):

product

5

was collected as

a

white solid (14.2 g, 93%). ¹H NMR

(CH₃)₃), 3.81 (s, 6H;

(500 MHz, CDCl₃, TMS): d=0.25 (s, 18H; SiACHTUNGTRENNNUG

OCH₃), 6.89 ppm (s, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=

0.4, 56.8, 101.2, 113.8, 116.6, 154.6 ppm; MS (ESI-TRAP): m/z: 330.14

[M]⁺.

Compound 6:^[21]K₂CO₃(15.0 g, 108 mmol) was added to a solution of 5

(4.55 g, 13.7 mmol) in

a mixture of CH₂Cl₂(150 mL) and MeOH

(150 mL). The reaction mixture was stirred for 4 h at room temperature.

Most of the solvent was removed in vacuo and then H₂O (300 mL) was

added to the reaction mixture. A yellow suspension formed. The product

d=0.40 (s, 18H; SiACHTUNTRGNEUNG(CH₃)₃), 3.72 (s, 6H; OCH₃), 5.40 (s, 4H; OCH₂O),

7.59–7.61 (dd, J=6.4, 3.3 Hz, 2H; Ar-H), 8.29–8.31 ppm (dd, J=6.4,

3.3 Hz, 2H; Ar-H); ¹³C NMR (125 MHz, CD₂Cl₂, TMS): d=0.1, 57.6,

98.7, 99.4, 106.2, 115.1, 125.7, 126.6, 130.8, 151.5 ppm; MS (ESI-TRAP):

m/z: 440.16 [M]⁺.

6 was collected by filtration and washed with H₂O and MeOH (2.50 g,

1

ꢂ

98%). H NMR (500 MHz, CDCl₃, TMS): d=3.37 (s, 2H; C CH), 3.84

(s, 6H; OCH₃), 6.96 ppm (s, 2H; Ar-H); MS (ESI-TRAP): m/z: 186.04

[M]⁺.

Compound 12: K₂CO₃(7.62 g, 55.0 mmol) was added to a solution of 11

(12.1 g, 27.4 mmol) in

a mixture of CH₂Cl₂(300 mL) and MeOH

Compound 7: Methyl 4-iodobenzoate (10.5 g, 40.0 mmol), [PdACTHUNTRGNE(UNG PPh₃)₄]

(300 mL) purged with Ar. The reaction mixture was stirred for 4 h at

room temperature. Solvents were removed in vacuo to give a reddish-

orange residue, which was dissolved in CH₂Cl₂(350 mL), washed with

H₂O (2ꢃ200 mL), and dried (MgSO₄). The solvent was removed in

vacuo to afford an orange solid. Column chromatography (SiO₂: hexane/

EtOAc=1:1 to 2:1) was carried out to provide 12 (8.48 g, 96%).

¹H NMR (500 MHz, CD₂Cl₂, TMS): d=3.73 (s, 6H; OCH₃), 3.91 (s, 2H;

(0.46 g. 0.40 mmol), and CuI (0.16 g, 0.80 mmol) were added to a mixture

of iPr₂NH (15 mL) and DMF (100 mL). The mixture was purged with Ar

while stirring for 30 min before a solution of 6 (3.70 g, 20.0 mmol) in

DMF (40 mL) was slowly added. The reaction mixture was stirred for 8 h

at 808C. After cooling to room temperature, the insoluble material was

collected by filtration, and washed with H₂O (350 mL) and MeOH

(100 mL). The yellow solid was dissolved in CHCl₃(1200 mL), washed

with H₂O (300 mL), and dried (MgSO₄). The solvent was removed in

ꢂ

C CH), 5.39 (s, 4H; OCH₂O), 7.60–7.63 (dd, J=6.3, 3.3 Hz, 2H; Ar-H),

8.32–8.34 ppm (dd, J=6.3, 3.3 Hz, 2H; Ar-H); ¹³C NMR (125 MHz,

CD₂Cl₂, TMS): d=57.7, 77.5, 88.1, 99.6, 114.5, 125.6, 126.7, 130.9,

151.9 ppm; MS (ESI-TRAP): m/z: 296.07 [M]⁺.

1

vacuo to afford the product 7 (8.38 g, 92%). H NMR (500 MHz, CDCl₃,

TMS): d=3.91 (s, 6H; OCH₃), 3.93 (s, 6H; COOCH₃), 7.04 (s, 2H; Ar-

H), 7.61–7.63 (d, J=8.4 Hz, 4H; Ar-H), 8.01–8.04 ppm (d, J=8.4 Hz,

4H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=52.1, 56.4, 88.4, 94.3,

113.2, 115.5, 127.7, 129.4, 129.5, 131.5, 153.9, 166.4 ppm; HRMS (ESI-

Compound 13: Methyl 4-iodobenzoate (10.6 g, 40.4 mmol), [PdACHTUNGTRENNUNG(PPh₃)₄]

(0.38 g. 0.37 mmol), CuI (0.14 g, 0.74 mmol), PPh₃(0.20 g, 0.47 mmol),

iPr₂NH (45 mL), and Et₃N (100 mL) were added to a three-necked flask

equipped with a condenser and a magnetic stirrer under an inert atmos-

phere. The mixture was purged with Ar followed by stirring for 30 min

before 12 (6.00 g, 20.2 mmol) was added. The reaction mixture was

slowly heated to 808C and stirred for 8 h at this temperature. After cool-

ing to room temperature, the insoluble material was removed by filtra-

tion and then rinsed with CH₂Cl₂(250 mL). The solution in CH₂Cl₂was

combined with the filtrate, and the organic phase was washed with H₂O

(2ꢃ100 mL) and dried (MgSO₄). The solvent was removed in vacuo to

afford the product 13 (8.30 g, 73%). ¹H NMR (500 MHz, CDCl₃, TMS):

d=3.73 (s, 6H; OCH₃), 3.96 (s, 6H; COOCH₃), 5.46 (s, 4H; OCH₂O),

7.61–7.63 (dd, J=6.4, 3.0 Hz, 2H; Ar-H), 7.71–7.73 (d, J=8.4 Hz, 4H;

Ar-H), 8.08–8.10 (d, J=8.4 Hz, 4H; Ar-H), 8.59–8.62 ppm (dd, J=6.4,

3.0 Hz, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=52.5, 58.2,

87.4, 99.8, 100.0, 115.6, 126.2, 127.2, 127.9, 129.9, 130.2, 131.1, 131.7,

151.5, 166.7 ppm; MS (ESI-TRAP): m/z: 564.21 [M]⁺.

+

TOF): m/z calcd for C₂₈H₂₃O₆[M+H]⁺: 455.1489; found: 455.1492.

Compound 8: 7 (1.00 g, 2.20 mmol) and NaOH (0.35 g, 8.80 mmol) were

dissolved in a mixture of THF (50 mL) and H₂O (50 mL). The solution

was stirred at room temperature overnight. The pH of the solution was

then adjusted to

formed, which was collected by filtration, washed with H₂O, and dried in

air to afford the product

(0.92 g, 98%). ¹H NMR (500 MHz,

2 with aqueous HCl solution (1m). A precipitate

8

CD₃SOCD₃, TMS): d=3.87 (s, 6H; OCH₃), 7.25 (s, 2H; Ar-H), 7.65–7.67

(d, J=8.5 Hz, 4H; Ar-H), 7.97–7.99 (d, J=8.5 Hz, 4H; Ar-H), 13.18 ppm

(s, 2H; COOH); ¹³C NMR (125 MHz, CD₃SOCD₃, TMS): d=56.7, 89.0,

94.4, 112.8, 116.0, 127.0, 129.9, 131.0, 131.8, 154.0, 167.9 ppm; HRMS

+

(ESI-TOF): m/z calcd for C₂₆H₁₉O₆

[M+H]⁺: 427.1176; found:

427.1176.

Compound 9: A solution of Br₂(40.6 g, 124 mmol) in AcOH (65 mL)

was gradually added to a stirred solution of naphthalene-2,3-diol (20.0 g,

124 mmol) in AcOH (85 mL). The reaction mixture was stirred overnight

at room temperature to form a white suspension. The solid was filtered,

washed with H₂O (300 mL), and dried in air. The product 9 was purified

by recrystallization from CHCl₃(32.0 g, 81%). ¹H NMR (500 MHz,

Compound 14: Compound 13 (2.50 g, 4.43 mmol) and NaOH (0.71,

17.7 mmol) were dissolved in a mixture of THF (100 mL) and H₂O

(100 mL). The reaction and purification procedures were identical to

Chem. Eur. J. 2009, 15, 13356 – 13380

ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

13373

J. F. Stoddart et al.

those described for the preparation of 8. The product 14 was a yellow

solid (2.25 g, 95%). ¹H NMR (500 MHz, CD₃SOCD₃, TMS): d=3.63 (s,

6H; OCH₃), 5.38 (s, 4H; OCH₂O), 7.68–7.70 (dd, J=6.2, 3.2 Hz, 2H; Ar-

H), 7.79–7.81 (d, J=8.0 Hz, 4H; Ar-H), 8.03–8.05 (d, J=8.0 Hz, 4H; Ar-

H), 8.32–8.35 (dd, J=6.2, 3.2 Hz, 2H; Ar-H), 13.20–13.22 ppm (b, 2H;

COOH); ¹³C NMR (125 MHz, CDCl₃, TMS): d=52.5, 58.2, 87.4, 99.8,

100.0, 115.6, 126.2, 127.2, 127.9, 129.9, 130.7, 131.1, 131.7, 151.5,

166.7 ppm; MS (ESI-TRAP): m/z: 536.09 [M]⁺.

Compound 15:^[21]Veratrol (40.0 g, 0.29 mol) was dissolved in a mixture

of dry hexane (100 mL) and TMEDA (40 mL). nBuLi (1.6m in hexane,

200 mL, 0.32 mol) was added dropwise at room temperature. The reac-

tion was stirred at room temperature for 28 h and cooled to À788C.

ClSiMe₃(45 mL) was added slowly and the reaction mixture was allowed

to warm to room temperature over 5 h. H₂O was added and the reaction

mixture was extracted with hexane. The organic layer was separated and

dried (MgSO₄). Solvent was removed in vacuo and the residue was puri-

fied by flash chromatography (SiO₂: hexane/CH₂Cl₂=10:1) to give the

product 15 as a colorless oil (51.5, 85%). ¹H NMR (500 MHz, CDCl₃,

mixture was purged with Ar followed by stirring for 30 min, and 2

(4.81 g, 30.0 mmol) was then added in one portion. After addition, the re-

action mixture was slowly heated to 808C and stirred for 8 h at this tem-

perature. After cooling to room temperature, the insoluble material was

collected by filtration and washed with Et₃N (30 mL). The solid was ex-

tracted with CH₂Cl₂(250 mL), washed twice with H₂O (2ꢃ150 mL). The

organic layer was dried (MgSO₄) and the solvent was removed in vacuo

to give the product 20 (6.50 g, 84%). ¹H NMR (500 MHz, CDCl₃, TMS):

d=3.67 (s, 6H; OCH₃), 3.93 (s, 6H; COOCH₃), 5.33 (s, 4H; OCH₂O),

7.28, (s, 2H; Ar-H), 7.58–7.59 (d, 4H; Ar-H), 8.02–8.04 ppm (d, 4H; Ar-

H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=52.3, 57.8, 57.3, 88.4, 94.4,

99.3, 119.4, 127.5, 128.6, 129.6, 129.8, 131.4, 151.2, 166.4 ppm; MS (ESI-

TRAP): m/z: 514.14 [M]⁺.

Compound 21: p-Toluenesulfonic acid (0.50 g, 2.91 mmol) was added to a

solution of 20 (1.70 g, 3.30 mmol) in a mixture of CH₂Cl₂(150 mL) and

MeOH (100 mL). The reaction mixture was stirred for 6 d at room tem-

perature to give a grey suspension. The precipitate was collected by fil-

tration, washed with H₂O, MeOH, and CH₂Cl₂, and dried in air to give

compound 21 (1.10 g, 78%). ¹H NMR (500 MHz, CDCl₃, TMS): d=3.94

(s, 6H; COOCH₃), 5.37 (s, 2H; OH), 7.24, (s, 2H; Ar-H), 7.58–7.60 (d,

4H; Ar-H), 8.02–8.04 ppm (d, 4H; Ar-H); ¹³C NMR (125 MHz, CDCl₃,

TMS): d=51.8, 88.3, 94.6, 119.2, 127.1, 128.2, 129.6, 129.9, 131.6, 132.4,

148.5, 166.4 ppm; MS (ESI-TRAP): m/z: 426.13 [M]⁺.

TMS): d=0.38 (s, 9H; SiACTHNUTRGNEUNG(CH₃)₃), 3.76 (s, 6H; OCH₃), 6.79–6.80 (d, 1H;

Ar-H), 6.81–6.82 (d, 1H; Ar-H), 6.84–6.85 ppm (d, 1H; Ar-H).

Compound 16: Compound 15 (69.0 g, 0.33 mol) was dissolved in

TMEDA (60 mL) and cooled to 08C. nBuLi in hexane (1.6m, 250 mL,

0.40 mol) was added dropwise. The reaction mixture was stirred at room

temperature for 25 h and then cooled to À788C. After ClSiMe₃(60 mL)

was added dropwise, the reaction mixture was warmed to room tempera-

ture over 5 h. H₂O was added and the reaction mixture was extracted

with hexane. The organic layer was separated and dried (MgSO₄). Sol-

vent was removed in vacuo and the residue was purified by flash chroma-

tography (SiO₂: hexane/CH₂Cl₂=10:1) to give the product 16 as a color-

less oil (82.5 g, 89%). ¹H NMR (500 MHz, CDCl₃, TMS): d=0.39 (s,

Compounds 22 and 23:^[24]

A suspension of pyrocatechol (3.20 g,

29.1 mmol), tetraethyleneglycol monotosylate (15.5 g, 44.5 mmol), and

K₂CO₃(11.0 g) in MeCN (350 mL) was stirred under reflux in an atmos-

phere of Ar for 2 d. After cooling to room temperature, the insoluble

materials were filtered off to give a light-yellow filtrate. It was dried

under reduced pressure to give 22 as a yellow oil, which was treated di-

rectly with tosyl chloride (9.25 g, 48.7 mmol) in THF (45 mL) in the pres-

ence of an aqueous solution of NaOH (4.11 g, 103 mmol). The resulting

mixture was stirred for another day. THF was removed under reduced

pressure and the H₂O phase was extracted twice with CH₂Cl₂(2ꢃ

150 mL). The organic phase was washed once with a saturated aqueous

solution of NaHCO₃(100 mL), twice with H₂O (150 mL), and dried

(MgSO₄). The solvent was removed under reduced pressure to give a

yellow residue. It was purified by flash column chromatography (SiO₂:

EtOAc/MeOH=98:2) to give the product 23 (10.2 g, 62%). ¹H NMR

(500 MHz, CDCl₃, TMS): d=2.45 (s, 6H; CH₃), 3.59–3.62 (m, 8H;

OCH₂CH₂O), 3.65–3.69 (m, 8H; OCH₂CH₂O), 3.75–3.77 (m, 4H;

OCH₂CH₂O), 3.93–3.95 (m, 4H; OCH₂CH₂O), 4.11–4.14 (m, 4H;

OCH₂CH₂O), 4.25–4.28 (m, 4H; OCH₂CH₂O), 6.90–6.91 (d, 2H; Ar-H),

6.93–6.94 (d, 2H; Ar-H), 7.42–7.44 (d, 4H; Ar-H), 7.71–7.73 ppm (d, 4H;

Ar-H).

18H; SiACHTUNGTRENNUNG

(CH₃)₃), 3.77 (s, 6H; OCH₃), 6.86 ppm (s, 2H; Ar-H); ¹³C NMR

(125 MHz, CDCl₃, TMS): d=2.1, 56.8, 122.9, 128.1, 152.4 ppm.

Compound 17:^[22]Compound 16 (19.2 g, 68.1 mmol) was dissolved in

CH₂Cl₂(100 mL) and the solution was cooled to 08C. A solution of ICl

(23.1 g, 0.14 mol) in CH₂Cl₂(100 mL) was added slowly. The reaction

mixture was warmed to room temperature, stirred for 30 min, and

quenched with an aqueous solution of Na₂S₂O₃. The organic layer was

separated and dried (MgSO₄). The solvent was removed in vacuo and the

crude product was purified by flash chromatography (SiO₂: hexane/

CH₂Cl₂=10:1) to give 17 as a yellowish oil (21.5 g, 81%), which solidi-

fied slowly at room temperature. M.p. 46–478C. ¹H NMR (500 MHz,

CDCl₃, TMS): d=3.87 (s, 6H; OCH₃), 7.24 ppm (s, 2H; Ar-H); ¹³C NMR

(125 MHz, CDCl₃, TMS): d=60.8, 93.0, 135.5, 153.1 ppm.

Compound 18:^[22,23]Compound 17 (1.80 g, 4.62 mmol) was dissolved in

CH₂Cl₂(20 mL) and the solution was cooled to À788C. BBr₃(2 mL,

5.30 g, 21.2 mol) was added and the reaction mixture was warmed to

room temperature and was stirred for 14 h. The reaction was poured into

ice/H₂O and the mixture was extracted with EtOAc, and the organic

layer was separated and dried (Na₂SO₄). The solvent was removed in

vacuo and the residue was purified by flash chromatography (SiO₂,

CH₂Cl₂) to afford 18 as a white solid (1.50 g, 90%). ¹H NMR (500 MHz,

CDCl₃, TMS): d=5.61 (s, 2H; OH), 7.00 ppm (s, 2H; Ar-H); ¹³C NMR

(125 MHz, CDCl₃, TMS): d=83.6, 131.2, 143.1 ppm.

DB30C10DE (Scheme 4): A three-necked flask was equipped with a

magnetic stirrer, a condenser, and a funnel under an inert atmosphere.

The flask was charged with Cs₂CO₃(7.50 g, 23.0 mmol) and DMF

(200 mL), and the reaction mixture was heated to 1008C. A solution of

compounds 21 (1.70 g, 4.00 mmol) and 23 (3.08 g, 4.00 mmol) in DMF

(150 mL) was added slowly to the stirring Cs₂CO₃suspension within 5 h.

After addition, the reaction mixture was stirred for 2 d at this tempera-

ture. When cooling to room temperature, the reaction mixture was fil-

tered to remove the insoluble material, and the solid was washed with

DMF (50 mL). The filtrates were combined together and solvent was re-

moved under reduced pressure to obtain a dark residue. The product was

purified by flash column chromatography (SiO₂: EtOAc) to give the

product DB30C10DE (0.55 g, 16%). ¹H NMR (500 MHz, CDCl₃, TMS):

d=3.65–4.12 (m, 38H; OCH₂O and COOCH₃), 6.82–6.83 (d, 2H; Ar-H),

6.91–6.92 (d, 2H; Ar-H), 7.31 (s, 2H; Ar-H), 7.67–7.69 (d, J=8.2 Hz, 4H;

Ar-H), 7.97–7.98 ppm (d, J=8.2 Hz, 4H; Ar-H); ¹³C NMR (125 MHz,

CDCl₃, TMS): d=52.2, 68.5, 69.3, 70.4, 70.7, 70.9, 87.2, 94.9, 113.3, 121.1,

124.8, 127.2, 129.9, 131.7, 148.1, 151.3, 166.5 ppm; HRMS (ESI-TOF): m/

Compound 19: A solution of iPr₂NH (12.5 mL, 72.0 mmol) in dry THF

(20 mL) was added slowly to a solution of 18 (10.9 g, 30.0 mmol) in dry

THF (100 mL) under an Ar atmosphere. The reaction mixture was stirred

for 30 min at room temperature and then ClCH₂OMe (5.80 g. 5.5 mL,

72.0 mmol) was added by means of a syringe. The resulting mixture was

stirred overnight at room temperature. The insoluble ammonium salts

were filtered off to give a light-yellow filtrate. The filtrate was dried

under vacuum to obtain

a

beige powder (13.4 g, 95%). ¹H NMR

(500 MHz, CDCl₃, TMS): d=3.67 (s, 6H; OCH₃), 5.41 (s, 4H; OCH₂O),

7.12 ppm (s, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS): 55.4, 94.6,

86.1, 132.9, 154.3 ppm; MS (ESI-TRAP): m/z: 449.85 [M]⁺.

+

z calcd for C₄₈H₅₃O₁₄[M+H]⁺: 853.3435; found: 853.3431.

DB30C10DA: A solution of NaOH (0.45 g, 11.0 mmol) in H₂O (30 mL)

was added to a solution of DB30C10DE (0.79 g, 0.93 mmol) in THF

(40 mL). The reaction mixture was stirred overnight at room tempera-

ture. THF was removed under reduced pressure to give dark-yellow resi-

due, which was acidified by 2n HCl aqueous (20 mL), forming a yellow

Compound 20: Compound 19 (6.75 g, 15.0 mmol), [PdACTHUNTRGNE(UNG PPh₃)₄] (0.29 g,

0.39 mmol), CuI (0.11 g, 0.56 mmol)), PPh₃(0.15 g, 0.57 mmol), iPr₂NH

(28 mL), and Et₃N (80 mL) were added to a three-necked flask equipped

with a condenser and a magnetic stirrer under an inert atmosphere. The

13374

www.chemeurj.org

ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eur. J. 2009, 15, 13356 – 13380

Rigid-Strut-Containing Crown Ethers and Catenanes

FULL PAPER

suspension. The yellow precipitate was collected by filtration and washed

with H₂O. The crude product was recrystallized from Me₂CO/MeOH to

yield DB30C10DA as

8H; OCH₂CH₂O), 3.66–3.68 (m, 8H; OCH₂CH₂O), 3.76–3.78 (m, 4H;

OCH₂CH₂O), 3.93–3.95 (m, 4H; OCH₂CH₂O), 4.12–4.15 (m, 4H;

OCH₂CH₂O), 4.27–4.29 (m, 4H; OCH₂CH₂O), 7.16 (s, 2H; Ar-H), 7.31–

7.34 (m, 6H; Ar-H), 7.65–7.67 (d, 2H; Ar-H), 7.78–7.79 ppm (d, 4H; Ar-

H).

a

yellow powder (0.70 g, 91%). ¹H NMR

(500 MHz, CD₃SOCD₃, TMS): d=3.71–4.22 (m, 32H; OCH₂O), 6.84–

6.85 (d, 2H; Ar-H), 6.86–6.87 (d, 2H; Ar-H), 7.31 (s, 2H; Ar-H), 7.67–

7.68 (d, J=8.3 Hz, 4H; Ar-H), 7.98–7.99 ppm (d, J=8.3 Hz, 4H; Ar-H);

¹³C NMR (125 MHz, CD₃SOCD₃, TMS): d=69.5, 70.3, 70.5, 70.8, 86.7,

95.1, 112.6, 120.9, 124.5, 127.3, 129.9, 132.2, 148.2, 150.8, 168.7 ppm;

DN30C10DE (Scheme 6): A three-necked flask was equipped with a

magnetic stirrer, a condenser, and a funnel under an inert atmosphere.

The flask was charged with Cs₂CO₃(2.74 g, 8.00 mmol) and DMF

(150 mL), and the reaction mixture was heated to 1008C. A solution of

compounds 25 (1.00 g, 2.10 mmol) and 27 (1.72 g, 2.10 mmol) in DMF

(100 mL) was added slowly with stirring to the Cs₂CO₃suspension within

5 h. After the addition, the reaction mixture was stirred for 2 d at this

temperature. On cooling to room temperature, the reaction mixture was

filtered to remove the insoluble material and the solid was washed with

DMF (50 mL). The filtrates were combined and the solvent was removed

under reduced pressure to give a dark residue. The product was purified

by flash column chromatography (SiO₂: EtOAc) to give the product

+

HRMS (ESI-TOF): m/z calcd for C₄₆H₄₉O₁₄[M+H]⁺: 825.3122; found:

825.3119.

Compound 24: A three-necked flask was equipped with a magnetic stir-

rer, a condenser, and a funnel under an inert atmosphere. The flask was

charged with Cs₂CO₃(7.50 g, 23.0 mmol) and DMF (200 mL), and the re-

action mixture was heated to 1008C. A solution of compounds 18 (1.45 g,

4.00 mmol) and 23 (3.08 g, 4.00 mmol) in DMF (150 mL) was added

slowly with stirring during 5 h to the Cs₂CO₃suspension. After the addi-

tion, the reaction mixture was stirred for a further 2 d at this tempera-

ture. On cooling to room temperature, the reaction mixture was filtered

to remove the insoluble material, and the solid was washed with DMF

(50 mL). The filtrates were combined and the solvent was removed

under reduced pressure to obtain a dark residue. The product was puri-

fied by flash column chromatography (SiO₂: EtOAc/hexane=3:1) to give

the product 24 (1.06 g, 34%). ¹H NMR (500 MHz, CDCl₃, TMS): d=

3.66–4.07 (m, 32H; OCH₂O), 6.91–6.92 (d, 2H; Ar-H), 6.93–6.94 (d, 2H;

Ar-H), 7.11 ppm (s, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=

68.5, 69.4, 69.5, 70.3, 70.9, 86.2, 120.7, 121.3, 131.6, 150.8, 152.2 ppm;

1

DN30C10DE (0.30 g, 15%). H NMR (500 MHz, CDCl₃, TMS): d=3.41–

4.18 (m, 38H; OCH₂O and COOCH₃), 7.26–7.28 (m, 4H; Ar-H), 7.66–

7.70 (m, 4H; Ar-H), 7.82–7.83 (d, 4H; Ar-H), 8.03–8.04 (d, 4H; Ar-H),

8.32–8.34 ppm (d, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=

52.3, 69.1, 69.6, 70.4, 70.9, 94.3, 101.4, 107.2, 124.5, 127.1, 129.8, 130.7,

132.6, 135.1, 150.0, 154.4, 166.1 ppm; HRMS (ESI-TOF): m/z calcd for

+

C₅₆H₅₇O₁₄[M+H]⁺: 953.3748; found: 953.3750.

DN30C10DA: A solution of NaOH (0.55 g, 13.8 mmol) in H₂O (40 mL)

was added to a solution of DN30C10DE (0.92 g, 0.97 mmol) in THF

(40 mL). The reaction mixture was stirred overnight at room tempera-

ture. THF was removed under reduced pressure to give a dark-yellow

residue, which was acidified by a 2n aqueous solution of HCl (20 mL) to

form a yellow suspension. The yellow precipitate was collected by filtra-

tion and washed with H₂O. The crude product was recrystallized from

Me₂CO/MeOH to yield DN30C10DA as a yellow powder (0.75 g, 84%).

¹H NMR (500 MHz, CD₃SOCD₃, TMS): d=3.53–4.20 (m, 32H;

OCH₂O), 7.25–7.28 (m, 4H; Ar-H), 7.69–7.71 (m, 4H; Ar-H), 7.81–7.83

(d, 4H; Ar-H), 8.04–8.05 (d, 4H; Ar-H), 8.31–8.33 ppm (d, 2H; Ar-H);

¹³C NMR (125 MHz, CD₃SOCD₃, TMS): d=68.9, 69.7, 70.5, 70.9, 71.2,

94.1, 101.4, 106.7, 124.9, 127.1, 128.3, 130.5, 132.7, 135.1, 150.5, 154.3,

+

HRMS (ESI-TOF): m/z calcd for C₂₈H₃₉I₂O₁₀[M+H]⁺: 789.0633;

found: 789.0628.

DB30C10DE (Scheme 5): Compound 24 (1.02 g, 1.30 mmol), [PdACHTNUTRGNE(UNG PPh₃)₄]

(26.0 mg, 0.02 mmol), CuI (10.0 mg, 0.05 mmol), PPh₃(15.0 mg,

0.06 mmol), iPr₂NH (5 mL), Et₃N (15 mL), and THF (15 mL) were

added to a three-necked flask equipped with a condenser and a magnetic

stirrer under an inert atmosphere. The mixture was purged with Ar while

stirring for 30 min, and 2 (0.42 g, 3.20 mmol) was added in one portion.

After completing this addition, the reaction mixture was slowly heated to

808C and stirred for 8 h at this temperature. After cooling to room tem-

perature, the insoluble material was collected by filtration. The solid was

extracted with CH₂Cl₂(100 mL) and the organic solution was washed

twice with H₂O (2ꢃ100 mL) and dried (MgSO₄). After removal of the

solvent, the pure product was obtained by recrystallization from CH₂Cl₂/

hexane (0.90 g, 89%).

+

170.2 ppm; HRMS (ESI-TOF): m/z calcd for C₅₄H₅₃O₁₄[M+H]⁺:

925.3435; found: 925.3431.

Compound 28: A three-necked flask was equipped with a magnetic stir-

rer, a condenser, and a funnel under an inert atmosphere. The flask was

charged with Cs₂CO₃(8.20 g, 25.0 mmol) and DMF (250 mL), and the re-

action mixture was heated up to 1008C. A solution of compounds 9

(1.60 g, 5.00 mmol) and 27 (4.10 g, 5.00 mmol) in DMF (300 mL) was

added slowly to the stirred Cs₂CO₃suspension during 5 h. After the addi-

tion, the reaction mixture was stirred for 2 d at this temperature. After

cooling to room temperature, the reaction mixture was filtered to remove

the insoluble material, and the solid was washed with DMF (50 mL). The

filtrates were combined and the solvent was removed under reduced

pressure to obtain a dark residue, which was purified by flash column

chromatography (SiO₂: hexane/EtOAc=1:3) to give the product 28

Compound 25: p-Toluenesulfonic acid (0.50 g, 2.91 mmol) was added to a

solution of 13 (1.86 g, 3.30 mmol) in a mixture of CH₂Cl₂(150 mL) and

MeOH (100 mL). The reaction mixture was stirred for 5 d at room tem-

perature to give a yellow suspension. The yellow solid was collected by

filtration, washed with H₂O and MeOH, and finally dried in air to give

1

the product 25 (1.30 g, 83%). H NMR (500 MHz, CDCl₃, TMS): d=3.89

(s, 6H; COOCH₃), 7.50–7.52 (d, 2H; Ar-H), 7.85–7.86 (d, J=8.4 Hz, 4H;

Ar-H), 8.03–8.05 (d, J=8.4 Hz, 4H; Ar-H), 8.15–8.17 ppm (d, 2H; Ar-

H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=52.2, 94.1, 104.8, 124.9, 126.5,

127.2, 130.0, 133.1, 133.7, 148.5, 166.2 ppm; MS (ESI-TRAP): m/z: 476.09

[M]⁺.

1

(1.56 g, 39%). H NMR (500 MHz, CDCl₃, TMS): d=3.45–4.20 (m, 38H;

Compounds 26 and 27:^[24]A suspension of 2,3-dihydroxynaphthalene

OCH₂O and COOCH₃), 7.28–7.30 (m, 4H; Ar-H), 7.68–7.72 (m, 4H; Ar-

H), 8.33–8.35 ppm (d, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS):

d=69.2, 69.7, 70.5, 71.1, 104.3, 107.1, 124.8, 126.2, 126.8, 129.7, 150.4,

(3.20 g,

20.0 mmol),

tetraethyleneglycol

monotosylate

(15.5 g,

44.0 mmol), and K₂CO₃(11.1 g, 80.0 mmol) in MeCN (350 mL) was

stirred and heated under reflux in Ar for 2 d. After cooling to room tem-

perature, the insoluble materials were filtered off to give a light-yellow

filtrate. It was dried under reduced pressure to give 26 as a yellow oil,

which was treated directly with tosyl chloride (9.25 g, 49.0 mmol) in THF

(45 mL) in the presence of an aqueous solution of NaOH (4.12 g,

103 mmol). The resulting mixture was stirred for another day. THF was

removed under reduced pressure and the H₂O phase was extracted twice

with CH₂Cl₂(2ꢃ150 mL). The organic phase was washed once with a sa-

turated aqueous solution of NaHCO₃(100 mL), twice with H₂O

(150 mL), and dried (MgSO₄). The solvent was removed reduced pres-

sure to give a yellow residue. It was purified by flash column chromatog-

raphy (SiO₂: EtOAc/MeOH=98:2) to give the product 27 (10.2 g, 62%).

¹H NMR (500 MHz, CDCl₃, TMS): d=2.43 (s, 6H; CH₃), 3.58–3.60 (m,

+

154.6 ppm; HRMS (ESI-TOF): m/z calcd for C₃₆H₄₃Br₂O₁₀[M+H]⁺:

793.1223; found: 793.1218.

DN30C10DE (Scheme 7): Compound 28 (1.27 g, 1.60 mmol), [PdACHTUNGTRENNUNG(PPh₃)₄]

(30.0 mg, 0.03 mmol), CuI (10 mg, 0.05 mmol), PPh₃(15.0 mg, 0.06 ppm),

iPr₂NH (5 mL), Et₃N (15 mL), and DMF (15 mL) were added to a three-

necked flask equipped with a condenser and a magnetic stirrer under an

inert atmosphere. The mixture was purged with Ar while stirring for

30 min, and 2 (0.52 g, 3.20 mmol) was added in one portion. After the ad-

dition, the reaction mixture was slowly heated to 1008C and stirred for

8 h at this temperature. After cooling to room temperature, the insoluble

material was collected by filtration. The solid was extracted with CH₂Cl₂

(100 mL), and the organic layer was washed twice with H₂O (2ꢃ100 mL)

Chem. Eur. J. 2009, 15, 13356 – 13380

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13375

J. F. Stoddart et al.

and dried (MgSO₄). After removal of solvent, the product was recrystal-

lized from CH₂Cl₂/hexane to give DN30C10DE (1.10 g, 72%).

phere of Ar for 2 d. After cooling to room temperature, the insoluble

materials were filtered off to give a light-yellow filtrate. It was dried

under reduced pressure to give 32 as a yellow oil, which was treated di-

rectly with tosyl chloride (9.25 g, 48.7 mmol) in THF (45 mL) in the pres-

ence of an aqueous solution of NaOH (4.11 g, 103 mmol). The resulting

mixture was stirred for another day. THF was removed under reduced

pressure, and the H₂O phase was extracted twice with CH₂Cl₂(2ꢃ

150 mL). The organic phase was washed once with a saturated aqueous

solution of NaHCO₃(100 mL), twice with H₂O (150 mL), and dried

(MgSO₄). The solvent was removed under reduced pressure to give a

yellow residue. It was purified by flash column chromatography (SiO₂:

EtOAc/MeOH=98:2) to give the product 33 (12.3 g, 55%). ¹H NMR

(500 MHz, CD₂Cl₂, TMS): d=2.48 (s, 6H; CH₃), 3.58–3.87 (m, 24H;

OCH₂CH₂O), 4.15–4.21 (m, 8H; OCH₂CH₂O), 6.79 (s, 4H; Ar-H), 7.40–

7.41 (d, 4H; Ar-H), 7.81–7.82 ppm (d, 4H; Ar-H).

Compound 29:

A

solution of 2,5-dibromohydroquinone (9.38 g,

35.0 mmol) and K₂CO₃(19.3 g, 140 mmol) in MeCN (400 mL) was

heated under reflux in an inert atmosphere for 30 min. A solution of tet-

raethyleneglycol monotosylate (26.9 g, 77.0 mmol) in MeCN (40 mL) was

added dropwise to the mixture over 30 min. Stirring and heating were

continued for 3 d. The reaction mixture was then filtered and the solvent

was removed in vacuo. The residue was purified by column chromatogra-

phy (SiO₂: CH₂Cl₂/MeOH=9:1) to yield compound 29 as a white solid

(13.7 g, 63%). ¹H NMR (500 MHz, CDCl₃, TMS): d=2.72–2.73 (b, 2H;

OH), 3.57–4.13 (m, 32H; OCH₂O), 7.14 ppm (s, 2H; Ar-H); ¹³C NMR

(125 MHz, CDCl₃, TMS): d=61.9, 69.8, 70.3, 70.5, 70.8, 71.3, 72.7, 111.6,

+

119.3, 150.4 ppm; HRMS (ESI-TOF): m/z calcd for C₂₂H₃₇Br₂O₁₀

[M+H]⁺: 619.0748; found: 619.0753.

Compound 34: Compound 33 (2.79 g, 3.62 mmol) and 2,5-dibromohydro-

quinone (0.97 g, 3.63 mmol) were dissolved in DMF (180 mL) in a flame-

dried, three-necked, round-bottomed flask. After Cs₂CO₃(2.37 g,

7.26 mmol) was added to the solution, the mixture was stirred under Ar

at 908C for 3 d. The solvent was removed in vacuo and the residue was

then dissolved in CH₂Cl₂(100 mL) before being washed with brine (3ꢃ

50 mL). The organic phase was dried (Na₂SO₄) and the solvent was then

removed in vacuo. Column chromatography (SiO₂: Et₂O/CH₂Cl₂=2:1)

was carried out to provide the product 34 as a white solid (0.65 g, 26%).

¹H NMR (500 MHz, CDCl₃, TMS): d=3.68–4.05 (m, 32H; OCH₂O), 6.74

(s, 4H; Ar-H), 7.07 ppm (s, 2H; Ar-H); ¹³C NMR (125 MHz, CDCl₃,

TMS): d=68.2, 69.6, 69.8, 70.3, 70.8, 70.9, 71.0, 71.1, 111.4, 115.6, 119.1,

Compounds 30 and 31: Compound 29 (3.10 g, 5.00 mmol), 2 (1.76 g,

11.0 mmol), [PdACHTUNGTRENNUNG(PPh₃)₄] (289 mg, 0.25 mmol), and CuI (47.5 mg,

0.25 mmol) were added to a mixture of Et₃N (50 mL) and DMF (50 mL).

The mixture was stirred at 908C for 3 d before the solvent was removed

in vacuo. The residue was then dissolved in CH₂Cl₂(50 mL) before Et₃N

(7.0 mL, 50 mmol), 4-dimethylaminopyridine (122 mg, 1.00 mmol), and a

solution of p-toluenesylfonyl chloride (2.29 g, 12.0 mmol) in CH₂Cl₂

(5 mL) were added into the solution. The solution was stirred for 3 h

before being washed with 1m aqueous HCl (100 mL) and H₂O (2ꢃ

100 mL), and then dried (MgSO₄). The solvent was then removed in

vacuo and the residue was purified by column chromatography (SiO₂:

CH₂Cl₂/EtOAc=2:1) to yield 31 as

a yellow solid (2.72 g, 50%).

+

¹H NMR (500 MHz, CDCl₃, TMS): d=2.42 (s, 6H; Ts-CH₃), 3.56–4.22

(m, 38H; OCH₂O and COOCH₃), 7.06 (s, 2H; Ar-H), 7.30–7.31 (d, J=

8.2 Hz, 4H; Ar-H), 7.58–7.59 (d, J=8.3 Hz, 4H; Ar-H), 7.78–7.79 (d, J=

8.2 Hz, 4H; Ar-H), 8.01–8.03 ppm (d, J=8.4 Hz, 4H; Ar-H); ¹³C NMR

(125 MHz, CDCl₃, TMS): d=20.6, 51.3, 67.6, 68.2, 68.5, 68.7, 69.5, 69.7,

70.1, 87.7, 93.5, 113.0, 116.2, 126.9, 128.5, 128.6, 128.8, 130.4, 131.9, 143.8,

150.3, 153.1 ppm; HRMS (ESI-TOF): m/z calcd for C₂₈H₃₉Br₂O₁₀

[M+H]⁺: 693.0904; found: 693.0902.

BPP34C10DE (Scheme 9): Compound 34 (0.10 g, 0.14 mmol) and

(0.05 g, 0.32 mmol) were dissolved in a mixture of DMF (3 mL) and

iPr₂NH (1 mL). Under Ar protection, [PdCl₂A(PPh₃)₂] (0.01 g, 0.014 mmol)

2

CTHUNGTRENNUNG

and CuI (0.003 g, 0.014 mmol) were added to the solution. The mixture

was stirred under Ar at 908C for 48 h before the solvent was removed in

vacuo. The residue was then dissolved in CH₂Cl₂(5 mL) before being

washed with H₂O (2ꢃ3 mL) and brine (3 mL). The organic phase was

dried (Na₂SO₄) and the solvent was then removed in vacuo. Column

chromatography (SiO₂: Et₂O/CH₂Cl₂=2:1) was carried out to provide

BPP34C10DE as a yellow fluorescent solid (0.10 g, 84%). ¹H NMR

(500 MHz, CDCl₃, TMS): d=3.64–4.13 (m, 38H; OCH₂O and

COOCH₃), 6.68 (s, 4H; Ar-H), 7.00 (s, 2H; Ar-H), 7.60–7.61 (d, J=

8.2 Hz, 4H; Ar-H), 8.01–8.02 ppm (d, J=8.2 Hz, 4H; Ar-H); ¹³C NMR

(125 MHz, CDCl₃, TMS): d=52.1, 68.0, 69.5, 69.6, 70.6, 70.7, 70.9, 71.0,

88.7, 94.5, 115.3, 117.0, 127.9, 129.4, 131.4, 152.9, 153.7, 166.4 ppm;

+

152.7, 165.5 ppm; HRMS (ESI-TOF): m/z calcd for C₅₆H₆₃O₁₈S₂

[M+H]⁺: 1087.3450; found: 1087.3477.

NPP36C10DE: A solution of 31 (820 mg, 0.76 mmol), 1,5-dihydroxy-

naphthalene (121 mg, 0.76 mmol), and Cs₂CO₃(984 mg, 3.02 mmol) were

dissolved in DMF (80 mL). The solution was stirred and heated under

reflux in an inert atmosphere for 3 d. The reaction mixture was filtered

and the solvent was removed. The resulting residue was purified by

column

NPP36C10DE as

chromatography

(SiO₂:

Et₂O/CH₂Cl₂=1:1)

to

yield

a

bright-yellow solid (136 mg, 20%). ¹H NMR

(500 MHz, CDCl₃, TMS): d=3.69–4.18 (m, 38H; OCH₂O and

COOCH₃), 6.66–6.67 (d, J=8.4 Hz, 2H; Ar-H), 6.84 (s, 2H; Ar-H), 7.22–

7.24 (t, J=8.4 Hz, 2H; Ar-H), 7.56–7.57 (d, J=8.4 Hz, 4H; Ar-H), 7.78–

7.79 (d, J=8.4 Hz, 2H; Ar-H), 8.00–8.02 ppm (d, J=8.4 Hz, 4H; Ar-H);

¹³C NMR (125 MHz, CDCl₃, TMS): d=52.3, 67.8, 68.2, 69.6, 69.7, 70.8,

70.9, 71.0, 88.9, 94.4, 105.5, 113.7, 114.5, 116.6, 125.0, 126.6, 128.0, 129.4,

129.5, 131.5, 153.5, 154.2, 166.6 ppm; HRMS (ESI-TOF): m/z calcd for

+

HRMS (ESI-TOF): m/z calcd for C₄₈H₅₃O₁₄[M+H]⁺: 853.3435; found:

853.3433.

BPP34C10DA: BPP34C10DE (0.20 g, 0.24 mmol) and KOH (0.05 mg,

0.94 mmol) were dissolved in a mixture of MeOH (10 mL), CH₂Cl₂

(10 mL), and THF (10 mL). The following reaction and purification pro-

cedures were identical to those described for the preparation of

NPP36C10DA. The product BPP34C10DA was a yellow solid (0.18 g,

94%). ¹H NMR (500 MHz, CDCl₃, TMS): d=3.63–4.13 (m, 32H;

OCH₂O), 6.67 (s, 4H; Ar-H), 6.99 (s, 2H; Ar-H), 7.57–7.58 (d, J=8.3 Hz,

4H; Ar-H), 8.04–8.05 (d, J=8.3 Hz, 4H; Ar-H), 13.23–13.24 ppm (b, 2H;

COOH); ¹³C NMR (125 MHz, CDCl₃, TMS): d=68.1, 69.6, 69.7, 69.8,

70.7, 70.8, 71.0, 71.1, 89.2, 94.6, 115.5, 117.2, 128.7, 128.8, 130.1, 131.6,

+

C₅₂H₅₅O₁₄[M+H]⁺: 903.3586; found: 903.3604.

NPP36C10DA: A solution of NPP36C10DE (130 mg, 0.14 mmol) and

KOH (78.4 mg, 1.40 mmol) were dissolved in

a mixture of MeOH

(2.5 mL) and CH₂Cl₂(2.5 mL). The solution was stirred overnight. The

reaction mixture was then filtered and solvent was removed. The residue

was purified by column chromatography (SiO₂: CH₂Cl₂/MeOH/AcOH=

9:1:0.01) to yield NPP36C10DA as a bright-yellow solid (121 mg, 96%).

¹H NMR (500 MHz, CD₃SOCD₃, TMS): d=3.53–4.10 (m, 32H;

OCH₂O), 6.71–6.73 (d, J=8.3 Hz, 2H; Ar-H), 7.09 (s, 2H; Ar-H), 7.21–

7.23 (t, J=8.3 Hz, 2H; Ar-H), 7.59–7.60 (d, J=8.4 Hz, 4H; Ar-H), 7.61–

7.62 (d, J=8.3 Hz, 2H; Ar-H), 7.93–7.94 (d, J=8.4 Hz, 4H; Ar-H), 12.8–

12.9 ppm (b, 2H; COOH); ¹³C NMR (125 MHz, CD₃SOCD₃, TMS): d=

68.1, 69.2, 69.3, 70.3, 70.4, 70.5, 70.6, 89.2, 94.7, 106.1, 113.4, 114.1, 116.8,

+

153.0, 153.9, 170.2 ppm; HRMS (ESI-TOF): m/z calcd for C₄₆H₄₉O₁₄

[M+H]⁺: 825.3122; found: 825.3115.

Compound 35: A three-necked flask was equipped with a magnetic stir-

rer, a condenser, and a funnel under an inert atmosphere. The flask was

charged with Cs₂CO₃(13.0 g, 40.0 mmol) and DMF (450 mL), and the re-

action mixture was heated up to 1008C. A solution of 2,5-diiodohydro-

quinone (2.90 g, 8.00 mmol) and 33 (6.17 g, 8.00 mmol) in DMF (300 mL)

was added slowly to the stirred Cs₂CO₃suspension within 5 h. After the

addition, the reaction mixture was stirred for 2 d at this temperature. On

cooling the solution to room temperature, the reaction mixture was fil-

tered to remove the insoluble material, and the solid was washed with

DMF (50 mL). The filtrates were combined and the solvent was removed

125.5, 126.3, 127.2, 129.9, 130.9, 131.7, 153.5, 154.1, 172.3 ppm; HRMS

+

(ESI-TOF): m/z calcd for C₅₀H₅₁O₁₄

[M+H]⁺: 875.3273; found:

875.3250.

Compounds 32 and 33:^[25]

A suspension of hydroquinone (3.20 g,

29.1 mmol), tetraethyleneglycol monotosylate (15.5 g, 44.5 mmol), and

K₂CO₃(11.0 g) in MeCN (350 mL) was stirred under reflux in an atmos-

13376

www.chemeurj.org

ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eur. J. 2009, 15, 13356 – 13380

Rigid-Strut-Containing Crown Ethers and Catenanes

FULL PAPER

under reduced pressure to obtain a dark residue. The product was puri-

fied by flash column chromatography (SiO₂: hexane/EtOAc=1:3) to give

the compound 35 (3.04 g, 48%). ¹H NMR (500 MHz, CDCl₃, TMS): d=

3.69–4.04 (m, 32H; OCH₂O), 6.75 (s, 4H; Ar-H), 7.10 ppm (s, 2H; Ar-

H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=68.1, 69.6, 70.0, 70.5, 70.7,

70.9, 71.1, 71.2, 86.1, 115.4, 120.3, 150.5, 152.8 ppm; HRMS (ESI-TOF):

at this temperature. After cooling to room temperature, the insoluble

material was collected by filtration, and then the solid was washed with

H₂O (350 mL) and extracted with CH₂Cl₂(300 mL). The organic layer

was washed twice with H₂O (2ꢃ150 mL) and dried (MgSO₄). After re-

moval of the solvent, the compound 39 was obtained (7.55 g, 83%).

¹H NMR (500 MHz, CDCl₃, TMS): d=1.59–2.03 (m, 12H; CH₂), 3.57–

3.62 (m, 2H; OCH₂), 3.94 (s, 6H; COOCH₃), 3.97 (s, 2H; OCH₂), 5.43–

5.44 (t, 2H; OCHO), 7.06 (s, 2H; Ar-H), 7.62–7.64 (d, J=8.4 Hz, 4H;

Ar-H), 8.02–8.04 ppm (d, J=8.4 Hz, 4H; Ar-H); ¹³C NMR (125 MHz,

CDCl₃, TMS): d=20.9, 26.1, 30.8, 52.0, 63.8, 87.3, 95.2, 103.6, 111.9,

118.5, 127.6, 129.3, 129.7, 131.8, 152.0, 166.1 ppm; HRMS (ESI-TOF): m/

+

m/z calcd for C₂₈H₃₉I₂O₁₀[M+H]⁺: 789.0633; found: 789.0630.

BPP34C10DE (Scheme 10): Compound 35 (2.85 g, 3.60 mmol), [Pd-

ACHTUNGTRENNUNG(PPh₃)₄] (80.0 mg, 0.07 mmol), CuI (30.0 mg, 0.16 mmol), PPh₃(45.0 mg,

0.17 mmol), iPr₂NH (7 mL), and Et₃N (25 mL) were added to a three-

necked flask, equipped with a condenser and a magnetic stirrer under an

inert atmosphere. The mixture was purged with Ar and stirred for

30 min, while compound 2 (1.38 g, 8.60 mmol) was added in one portion.

After the addition, the reaction mixture was slowly heated to 808C and

stirred for 8 h at this temperature. After cooling to room temperature,

the solvent was removed under reduced pressure to yield a yellowish-

orange residue, which was extracted with CH₂Cl₂(200 mL) and washed

twice with H₂O (2ꢃ150 mL). The organic layer was dried (MgSO₄).

After removal of solvent, the product was purified by flash column chro-

matography (SiO₂: hexane/EtOAc=1:3) to give BPP34C10DE (2.63 g,

87%).

+

z calcd for C₃₆H₃₅O₈[M+H]⁺: 595.2332; found: 595.2329.

Compound 40 (shown in Scheme 12): p-Toluenesulfonic acid (1.42 g,

8.27 mmol) was added to a solution of 39 (4.92 g, 8.27 mmol) in a mixture

of CH₂Cl₂(150 mL) and MeOH (100 mL). The reaction mixture was

stirred overnight at room temperature to give a yellow suspension. The

yellow precipitate was collected by filtration, washed by MeOH, and

dried to afford the compound 40 (3.38 g, 86%). ¹H NMR (500 MHz,

CDCl₃, TMS): d=3.92 (s, 6H; COOCH₃), 5.38 (s, 2H; OH), 7.09 (s, 2H;

Ar-H), 7.63–7.64 (d, J=8.4 Hz, 4H; Ar-H), 8.03–8.05 ppm (d, J=8.4 Hz,

4H; Ar-H); ¹³C NMR (125 MHz, CDCl₃, TMS): d=52.1, 85.8, 95.7,

115.2, 121.1, 127.3, 129.4, 129.9, 132.0, 152.4, 165.8 ppm; HRMS (ESI-

BPP34C10DE (Scheme 11): A solution of 31 (1.09 g, 1.00 mmol), hydro-

quinone (0.11 g, 1.00 mmol), and Cs₂CO₃(1.30 g, 4.00 mmol) in DMF

(100 mL) was stirred and heated under reflux in an inert atmosphere for

5 d. The reaction mixture was filtered and the filtrate was removed. The

residue was purified by column chromatography (SiO₂: Et₂O/CH₂Cl₂=

1:1) to yield BPP34C10DE as a yellow solid (0.20 g, 24%).

Compound 36:^[26]PPTS (100 mg, 0.40 mmol) was added to an Ar-blanket-

ed solution of 2,5-dibromohydroquinone (15.0 g, 56.0 mmol) in 3,4-dihy-

dro-2H-pyran (DHP; 20 mL). A mildly exothermic reaction ensued and

the suspension obtained was allowed to stir at room temperature for

12 h. Excess DHP was removed under vacuum and the residue was

quenched with a saturated aqueous solution of NaHCO₃(150 mL), ex-

tracted into CH₂Cl₂(2ꢃ500 mL), washed with H₂O (2ꢃ150 mL), and

dried (MgSO₄). The mixture was filtered through a pad of silica and the

solvent was removed to yield a cream-white solid. Recrystallization from

hexane/CH₂Cl₂afforded the compound 36 as an off-white solid (21.5 g,

88%). ¹H NMR (500 MHz, CDCl₃, TMS): d=1.64–1.73 (m, 8H; CH₂),

1.86–2.06 (m, 4H; CH₂), 3.60–3.64 (m, 2H; OCH₂), 3.91 (s, 2H; OCH₂),

5.38–5.39 (t, 2H; OCHO), 7.32 ppm (s, 2H; Ar-H).

+

TOF): m/z calcd for C₂₆H₁₉O₆[M+H]⁺: 427.1182; found: 427.1178.

BPP34C10DE (Scheme 12): A three-necked flask was equipped with a

magnetic stirrer, a condenser, and a funnel under an inert atmosphere.

The flask was charged with Cs₂CO₃(3.91 g, 12.0 mmol) and DMF

(250 mL), and the reaction mixture was heated to 1008C. A solution of

compounds 40 (1.28 g, 3.00 mmol) and 33 (2.31 g, 3.00 mmol) in DMF

(200 mL) was added slowly to the stirred Cs₂CO₃suspension within 5 h.

After the addition, the reaction mixture was stirred for 2 d at this temper-

ature. On cooling to room temperature, the reaction mixture was filtered

to remove the insoluble material, and the solid was washed with DMF

(50 mL). The filtrates were combined and the solvent was removed

under reduced pressure to give a dark residue. The product was purified

by flash column chromatography (SiO₂: hexane/EtOAc=1:3) to give

BPP34C10DE (0.26 g, 10%).

Compound 40 (shown in Scheme 13):

A solution of BBr₃(1.20 g,

4.80 mmol) in CH₂Cl₂(45 mL) was added dropwise to a solution of 7

(0.91 g, 2.00 mmol) in CH₂Cl₂(20 mL) at À788C under Ar. The reaction

mixture was warmed to room temperature and stirred overnight. When

the reaction mixture was poured into ice/H₂O (150 mL), it yielded a

yellow precipitate. The yellow solid was collected by filtration, washed

with H₂O and MeOH, and dried in air to give 40 as a yellow powder.

The ¹H NMR spectrum shows that this yellow powder is a mixture and

the target compound cannot be isolated under the current experimental

conditions.

Compound 37:^[26a]Ar was bubbled through a solution of iPr₂NH (38 mL)

and Et₃N (105 mL) for 30 min. Compound 36 (9.16 g, 21.0 mmol) fol-

lowed by CuI (0.15 g, 0.78 mmol), PPh₃(0.20 g, 0.75 mmol), and [Pd-

ACHTUNGTRENNUNG(PPh₃)₄] (0.40 g, 0.35 mmol) were added and allowed to stir at room tem-

perature for 30 min. Trimethylsilylacetylene (7.5 mL, 54.0 mmol) was

added and the mixture was heated at 808C for 6 h. The precipitates were

collected by filtration, and the solid was extracted with CH₂Cl₂and

washed twice with H₂O (2ꢃ250 mL). The organic layer was dried

(MgSO₄). After removal of solvent, the product 37 was obtained (8.20 g,

H₂NPP36C10DC-CAT·4PF₆: NPP36C10DA (52.5 mg, 0.06 mmol), 1,1’-

(1,4-phenylenebis(methylene))di-4,4’-bipyridin-1-ium bis(hexafluorophos-

phate) (84.8 mg, 0.12 mmol), and 1,4-bis(bromomethyl)benzene (15.8 mg,

0.06 mmol) were dissolved in DMF (2 mL). The mixture was stirred at

room temperature for 7 d and the solvent was then removed in vacuo.

Column chromatography (SiO₂: MeOH/NH₄Cl (2m)/MeNO₂=7:2:1) was

then performed to give a red product. H₂O was then added to dissolve

the residue. A saturated aqueous solution of NH₄PF₆was added to the

solution until the red precipitate stopped forming. The precipitate was

collected by filtration, washed with H₂O, EtOH, and Et₂O, and then

dried in air to provide H₂NPP36C10DC-CAT·4PF₆as a dark-red solid

(53.4 mg, 45%). ¹H NMR (500 MHz, CD₃SOCD₃, TMS): d=2.17–2.18

(d, 2H; DNP-H), 3.17–4.18 (m, 32H; OCH₂O), 5.65 (s, 8H; N⁺-CH₂),

6.07–6.09 (m, 2H; DNP-H), 6.18–6.20 (d, 2H; DNP-H), 6.44 (s, 2H; Ar-

H), 7.17–7.24 (m, 4H; Ar-H), 7.51 (s, 8H; C₆H₄), 7.88–7.98 (m, 4H; Ar-

H), 8.37–8.41 (m, 8H; b-H), 9.15–9.16 (b, 8H; a-H), 10.56–10.57 ppm (b,

2H; COOH); HRMS (ESI-TOF): m/z calcd for [M·2PF₆]²⁺: 842.2557;

found: 842.2549.

83%). ¹H NMR (500 MHz, CDCl₃, TMS): d=0.22 (s, 18H; Si

ACTHNUGTRNEUGN(CH₃)₃),

1.64–2.30 (m, 12H; CH₂), 3.60–3.63 (m, 2H; OCH₂), 3.95 (s, 2H; OCH₂),

5.46–5.47 (t, 2H; OCHO), 7.18 ppm (s, 2H; Ar-H).

Compound 38:^[26a]Compound 37 (12.2 g, 26.0 mmol) was dissolved in an

Ar-blanketed mixture of CH₂Cl₂(250 mL) and MeOH (100 mL), and

KOH (4.20 g, 76.0 mmol) was then added. The mixture was heated under

gentle reflux for 10 min and the solvent was removed under reduced

pressure. The residue was purified by flash column chromatography

(SiO₂: hexane/CH₂Cl₂=7:3) to yield the product 38 as a pale-yellow solid

(8.2 g, 87%). ¹H NMR (500 MHz, CDCl₃, TMS): d=1.60–2.05 (m, 12H;

CH₂), 3.36 (s, 2H; CCH), 3.58–3.64 (m, 2H; OCH₂), 3.96 (s, 2H; OCH₂),

5.43–5.44 (t, 2H; OCHO), 7.23 ppm (s, 2H; Ar-H).

Compound 39: Methyl 4-iodobenzoate (8.83 g, 33.7 mmol), [PdACTHUNTRGNE(UNG PPh₃)₄]

(0.29 g. 0.28 mmol), CuI (0.10 g, 0.52 mmol), PPh₃(0.15 g, 0.35 mmol),

iPr₂NH (28 mL), and Et₃N (75 mL) were added to a three-necked flask

equipped with a condenser and a magnetic stirrer under an inert atmos-

phere. The mixture was purged with Ar and stirred for 30 min, and com-

pound 38 (5.00 g, 15.3 mmol) was added in one portion. After the addi-

tion, the reaction mixture was slowly heated to 808C and stirred for 8 h

BPP34C10DE-CAT·4PF₆: BPP34C10DE (51.2 mg, 0.06 mmol), 1,1’-(1,4-

phenylenebis(methylene)) di-4,4’-bipyridin-1-ium (42.4 mg, 0.06 mmol),

and 1,4-bis(bromomethyl)benzene (15.8 mg, 0.06 mmol) were dissolved

in DMF (2 mL). The following reaction and purification procedures were

Chem. Eur. J. 2009, 15, 13356 – 13380

ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

13377

J. F. Stoddart et al.

identical to those described for the preparation of NPP36C10DA-

CAT·4PF₆. The product BPP34C10DE-CAT·4PF₆was obtained as a

dark-red solid (0.69 g, 55%). ¹H NMR (500 MHz, CD₃CN, TMS): d=

3.34–4.00 (m, 42H; OCH₂O, COOCH₃, and Ar-H), 5.66 (s, 8H; N⁺-

CH₂), 6.44 (s, 2H; Ar-H), 7.69–7.70 (d, J=8.3 Hz, 4H; Ar-H), 7.71–7.72

(d, J=6.6 Hz, 8H; b-H), 7.80 (s, 8H; C₆H₄), 8.14–8.15 (d, J=8.3 Hz, 4H;

Ar-H), 8.92–8.93 ppm (d, J=6.6 Hz, 8H; a-H); ¹³C NMR (125 MHz,

CD₃CN, TMS): d=52.1, 63.8, 66.0, 68.8, 69.6, 69.8, 70.6, 70.8, 71.2, 87.4,

95.5, 112.9, 116.0, 125.3, 130.0, 130.6, 131.9, 137.2, 144.7, 145.7, 149.8,

151.2, 151.5, 164.5 ppm; HRMS (ESI-TOF): m/z calcd for

MOF-1002: A solution of MeNH₂(50 mL, 40 wt% in H₂O) was mixed

with DMF (2 mL) as stock solution A. A solid mixture of NPP36C10DA

ACTHNUTRGNEUNG

(3.82 mg, 4.36ꢃ10^À6mol) and Zn(NO₃)₂·4H₂O (5.25 mg, 2.01ꢃ10^À5mol)

was dissolved in DMF (1.0 mL) in a 4 mL vial. Stock solution A (20 mL)

was added to the vial. The vial was capped and placed in an isothermal

oven at 658C for 24 h. The vial was then removed from the oven and al-

lowed to cool to room temperature naturally. After removal of the

mother liquor from the mixture, fresh DMF was added to the vial. Light-

yellow, cubic crystals of MOF-1002 were collected and rinsed with DMF

(4ꢃ1 mL). Yield: 75%; elemental analysis (evacuated) calcd (%) for

Zn₄O(C₅₀H₄₈O₁₄)₃: C 62.20, H 5.01; found: C 63.21, H 4.98.

+

C₈₄H₈₄F₁₈N₄O₁₄P₃[M·3PF₆]⁺: 1807.49; found: 1807.40.

CCDC-738436 (31), 742778 (BPP34C10DE), 738435 (NPP36C10DA),

H₂BPP34C10DC-CAT·4PF₆: BPP34C10DA (49.5 mg, 0.06 mmol), 1,1’-

(1,4-phenylenebis(methylene)) di-4,4’-bipyridin-1-ium bis(hexafluoro-

phosphate) (84.8 mg, 0.12 mmol), and 1,4-bis(bromomethyl)benzene

(15.8 mg, 0.06 mmol) were dissolved in DMF (2 mL). The following reac-

tion and purification procedures were identical to those described for the

728420

(DMBP·2PF₆ꢀBPP34C10DA),

738434

(BPP34C10DE-

CAT·4PF₆), 728415 and 728416 (MOF-1001), and 728419 (MOF-1002)

contain the supplementary crystallographic data for this paper. These

data can be obtained free of charge from The Cambridge Crystallograph-

ic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

preparation

of

H₂NPP36C10DC-CAT·4PF₆.

The

product

H₂BPP34C10DC-CAT·4PF₆was obtained as a dark-red solid (0.64 g,

55%). ¹H NMR (500 MHz, CD₃SOCD₃, TMS): d=3.37–3.87 (m, 36H;

OCH₂O and Ar-H), 5.67 (s, 8H; N⁺-CH₂), 6.41 (s, 2H; Ar-H), 7.55–7.56

(d, J=8.3 Hz, 4H; Ar-H), 7.85 (s, 8H; C₆H₄), 8.00–8.01 (d, J=8.3 Hz,

4H; Ar-H), 8.07–8.09 (b, 8H; b-H), 9.20–9.21 (b, 8H; a-H), 11.45–

11.46 ppm (b, 2H; COOH); ¹³C NMR (125 MHz, CD₃SOCD₃, TMS): d=

63.8, 66.0, 68.8, 69.6, 69.7, 69.9, 70.0, 70.5, 70.8, 87.6, 95.5, 112.4, 116.0,

125.3, 130.0, 130.7, 131.5, 137.1, 144.7, 145.5, 151.3, 152.4, 167.3,

Acknowledgements

This material is based upon work supported at Northwestern University

by the National Science Foundation under CHE-0924620. The work at

the University of California, Los Angeles was supported by the Depart-

ment of Energy (DE-FG36-05GO15001) and the Department of De-

fense/Defense Threat Reduction Agency (HDTRA1-08-10023).

+

169.7 ppm; HRMS (ESI-TOF): m/z calcd for C₈₂H₈₀F₁₈N₄O₁₄P₃

[M·3PF₆]⁺: 1779.46; found: 1779.41.

¹⁵N-Labeled DMBP·2PF₆: Under an inert atmosphere, CH₃I (4.67 g,

32.9 mmol) was added dropwise to ¹⁵N-labeled C₆H₅N (2.00 g,

25.3 mmol). The mixture was stirred at 508C for 12 h before MeOH

(0.5 mL) was added. The mixture was stirred for another 10 min before

the solvents were removed in vacuo. The resulting white solid was dis-

solved in a mixture of EtOH (8 mL), MeOH (8 mL), and H₂O (8 mL) to-

gether with NaCN (3.05 g, 63.2 mmol) and NaOH (1.21 g, 30.3 mmol).

The solution was heated to reflux for 30 min, and a dark-blue solution re-

sulted. After the solution had cooled to room temperature, ZnSO₄·7H₂O

(10.2 g, 35.4 mmol) was added and a precipitate started to form. The mix-

ture was kept at room temperature without stirring for 1 h before the

precipitate was removed by filtration. The pH of the filtrate was then ad-

justed to 5 with H₂SO₄. O₂was then bubbled into the solution for 12 h

while the temperature of the solution was maintained below 508C. The

color of the solution turned from violet to tan. A saturated aqueous solu-

tion of NH₄PF₆was then added until no more precipitate formed. The

precipitate was collected by filtration, washed with H₂O, EtOH, and

Et₂O, and then dried in air. The product was a white solid (3.90 g, 70%).

¹H NMR (500 MHz, CD₃COCD₃, TMS): d=4.76 (s, 6H; CH₃), 8.86–8.87

(d, J=6.5 Hz, 4H; b-H), 9.39–9.40 ppm (d, J=6.5 Hz, 4H; a-H);

¹³C NMR (125 MHz, CD₃COCD₃, TMS): d=52.2, 126.7, 146.5,

151.5 ppm; HRMS (ESI-TOF): m/z calcd for C₁₂H₁₄F₆N₂P⁺[M·PF₆]⁺:

331.079; found: 331.082.

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DMBP·2PF₆ꢀBPP34C10DA: BPP34C10DA (9.01 mg, 0.01 mmol) and

DMBP·2PF₆(4.76 mg, 0.01 mmol) were dissolved in Me₂CO (5 mL) in a

20 mL vial. n-Pentane was added to the solution until some precipitation

was observed. The mixture was filtered to obtain a saturated solution.

The solution was left at room temperature for 3 d, and the red, block-

shape crystals were observed on the vial wall and then collected for the

X-ray crystallographic analyses.

MOF-1001: A solution of MeNH₂(50 mL, 40 wt% in H₂O) was mixed

with DMF (2 mL) as stock solution A. A solid mixture of BPP34C10DA

ACTHNUTRGNEUNG

(3.60 mg, 4.36ꢃ10^À6mol) and Zn(NO₃)₂·4H₂O (5.25 mg, 2.01ꢃ10^À5mol)

was dissolved in DMF (1.0 mL) in a 4 mL vial. Stock solution A (20 mL)

was added to the vial. The vial was capped and placed in an isothermal

oven at 658C for 24 h. The vial was then removed from the oven and al-

lowed to cool to room temperature naturally. After removal of the

mother liquor from the mixture, fresh DMF was added to the vial. Light-

yellow, cubic crystals of MOF-1001 were collected and rinsed with DMF

(4ꢃ1 mL). Yield: 75%; elemental analysis (evacuated) calcd (%) for

Zn₄O(C₄₆H₄₆O₁₄)₃: C 60.36, H 5.07; found: C 59.49, H 5.07.

13378

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Chem. Eur. J. 2009, 15, 13356 – 13380

Rigid-Strut-Containing Crown Ethers and Catenanes

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Received: August 26, 2009

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Chem. Eur. J. 2009, 15, 13356 – 13380

Article Doi

Rigid-Strut-Containing crown ethers and [2]catenanes for incorporation into Metal-Organic frameworks

DOI: 10.1002/chem.200902350

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