Self-assembly of semifluorinated minidendrons attached to electron-acceptor groups into pyramidal columns

DOI: 10.1002/chem.200600901

Self-Assembly of Semifluorinated Minidendrons Attached to Electron-

Acceptor Groups into Pyramidal Columns

Virgil Percec,*^[a]Emad Aqad,^[a]Mihai Peterca,^[b]Mohammad R. Imam,^[a]

Martin Glodde,^[a]Tusha K. Bera,^[a]Yoshiko Miura,^[a]

Venkatachalapathy S. K. Balagurusamy,^{[a, b]}Paul C. Ewbank,^[a]Frank Würthner,^[c]and

Paul A. Heiney^[b]

Abstract: The synthesis and self-assem-

bly of twelve semifluorinated first-gen-

eration dendrons or minidendrons at-

tached to electron-acceptor (n-type)

groups generated from various combi-

nations of eight acceptors and three

dendrons are reported. Dendrons at-

tached to small electron-acceptor mole-

cules mediate their self-assembly into

p-stacks located in the center of a

the column. Dendrons attached to

large electron-acceptor molecules, such

as perylene bisimide, mediate the as-

sembly of their acceptors in an unpre-

cedented arrangement of p-stacks that

have the long axis of the acceptors par-

allel to the long axis of the supramolec-

ular pyramidal column. All supra-

molecular columns self-organize into

various periodic columnar arrays that

exhibit liquid-crystalline phases, crys-

talline phases, or a liquid-crystalline

phase with enhanced intracolumnar

order. The present study demonstrates

the simplicity and the versatility of the

concept of assembly of n-type electro-

active groups mediated by semifluori-

nated dendrons and assesses the scope

and limitations of this supramolecular

strategy.

Keywords:

electron-acceptor

dendrimers

groups

·

supramolecular

helical

pyramidal

column with the long axis of the ac-

ceptor perpendicular to the long axis of

liquid crystals · self-assembly

Introduction

processability but low charge-carrier mobility.^[1,3]Electrically

conducting hexagonal columnar liquid crystals (LC) exhibit

mobilities approaching those of single crystals.^[4]Moreover,

the LC phase allows the dynamic reorganization that is nec-

essary for defect repair, and also facilitates the processing of

single crystal LC monodomains of organic thin films that

are not accessible from organic single crystals. Early success

was found with electron-donor discotic mesogenes, which

form one-dimensional stacks that self-organize into colum-

nar hexagonal or rectangular lattices.^[5]Other liquid crystals

proved to be suitable, allowing material properties that can

match those required by applications.^[6]Notably, these meth-

ods rely on organizational preferences of the constituent

molecules. Many low-molar-mass donor and acceptor mole-

cules self-organize in a face-to-edge arrangement that does

not favor the transport of charge carriers. This arrangement

is overcome by electron-donor and electron-acceptor disk-

like electroactive molecules that self-organize into columnar

stacks with a favorable face-to-face orientation of the planar

and symmetric aromatic large cores. Although this process

yields supramolecular structures with efficient p–p stacking

and high charge-carrier mobilities, it restricts the choice of

Electrically conducting organic single crystals^[1a]and poly-

mers^[1]have emerged as promising candidates for use in

electronic and optoelectronic devices. Single-crystal organic

conductors have high charge-carrier mobilities but are usual-

ly impractical,^[2]whereas conducting polymers have good

[a] Prof. V. Percec, Dr. E. Aqad, M. R. Imam, Dr. M. Glodde,

Dr. T. K. Bera, Dr. Y. Miura, Dr. V. S. K. Balagurusamy,

Dr. P. C. Ewbank

Roy&Diana Vagelos Laboratories

Department of Chemistry, University of Pennsylvania

Philadelphia, Pennsylvania, 19104-6323 (USA)

Fax: ( +1)215-573-7888

E-mail: percec@sas.upenn.edu

[b] M. Peterca, Dr. V. S. K. Balagurusamy, Prof. P. A. Heiney

Department of Physics and Astronomy

University of Pennsylvania

Philadelphia, Pennsylvania, 19104-6323 (USA)

[c] Prof. F. Würthner

Institute of Organic Chemistry

University of Würzburg, 97074 Würzburg (Germany)

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Chem. Eur. J. 2007, 13, 3330 – 3345

FULL PAPER

conjugated molecules to a small group and also requires the

synthesis of complexdiscotic molecules.

sembly of electron-donor p-type molecules as a p-stack in

the center of a supramolecular helical column was dis-

cussed.

N-type discotic molecules are limited to selected examples

of electron acceptors such as hexaazatriphenylene,^[11]hexa-

azatriphenylenehexacarboxytriimide,^[12]hexaazatrinaphthy-

lene,^[13]tricycloquinazoline,^[14]perylene bisimide,^[15]and di-

and triazaheterocyles.^[16]In general, electron-deficient heter-

ocyles, such as hexaazatripheny-

The new area of supramolecular electronics, is emerging

at the interface between supramolecular chemistry, liquid

crystals, and molecular electronics, and provides the most

recent advance in organic electronic materials.^[7,8]Recently,

a novel concept for the creation of supramolecular ordered

electronic materials was reported (Figure 1).^[8a]It involves

lene, avoid p-complexation or

self-p–p interactions.^[17]The

weak self-p–p interaction ac-

counts for the limited number

of available self-assembling

electron-accepting discotic mes-

ogenes and suggests that other

interactions are required to en-

force p–p stacking. Indeed, it

has been found that hydrogen

bonding mediates the self-as-

sembly of the electron-accept-

ing hexacarboxamidohexaaza-

triphenylene to produce the

lowest

inter-disk

distance

Figure 1. Self-assembly and self-repair of electron-acceptor p-stacks mediated by a semifluorinated miniden-

dron attached to the acceptor group generates electronically active supramolecular helical pyramidal columns. (3.18 ) reported so far in col-

umnar liquid crystals.^[11c]Never-

theless, synthetic limitations of

the disk-shape acceptor mole-

the use of fluorinated tapered first-generation dendrons or

minidendrons, known to self-assemble into highly ordered

supramolecular columnar LCs. This concept was used to me-

diate the desired face-to-face arrangement of the electroac-

tive components that were attached at their apices.^[9]Nano-

meter-scale columns with a core of p-stacked donor, accep-

tor, or donor-acceptor complexes were generated by this

strategy. The hexagonal columnar phase (F_h) thus obtained,

can be transformed into a glassy F_hstate upon slow cooling

from the isotropic melt. In addition, this assembly mecha-

nism is equipped with a self-repair process that mediates the

correction of architectural defects and also allows the for-

mation of semiconductors that maintain the order of their

liquid-crystalline state after cooling below their glass transi-

tion.^[8a]

The fluorous phase of the dendron mediates the self-as-

sembly process my means of the fluorophobic effect^[10]and

also protects the electroactive core of the supramolecular

column, which contains a hydrophilic oligooxyethylene layer

on its periphery, from moisture.^[7f,g,8a]The electroactive moi-

eties are attached to the dendron by di- or tetraethylene

glycol spacers. These spacers decouple the motion of the

dendron and electroactive core and facilitate reorganization

and self-assembly. The co-assembly of electron-donor and

electron-acceptor functionalized dendrons with or without

complementary amorphous polymers paves the way for the

design and fabrication of various electronic functions of or-

ganic materials. In a recent publication,^[8b]the scope and

limitation of this architectural concept applied to the self-as-

cules limit the practical capabilities of this class of mole-

cules.

In a preliminary communication, it was demonstrated that

the attachment of the electron-acceptor 4,5,7-trinitro-9-fluo-

renone (TNF) at the apexof a first-generation semifluori-

nated dendron mediates the self-assembly of the TNF in the

center of a supramolecular helical column with an average

separation of 3.44 .^[8a]Preliminary results have shown that

this concept increases the charge-carrier mobility of the

electron-acceptor unit by up to five orders of magnitude.^[8a]

In the present study, the universality of this self-assembly

concept is addressed by adapting it to the self-assembly of

twelve dendronized electron-acceptor molecules. The effect

of small structural modifications of the spacer, dendron, and

electroactive core on the self-assembly process of five struc-

turally modified dendronized-TNF derivatives was investi-

gated in more details. A discussion of the scope and limita-

tions of the self-assembly of electron-acceptor molecules at-

tached to the apexof semifluorinated dendrons concludes

this report.

Results and Discussion

Synthesis: The structures of the dendrons with electron-ac-

cepting groups at their apexthat will be discussed in this

paper are shown in Figure 2. The synthesis of

(3,4,5)12F8G1-2EOTNF (A8) was reported previously.^[8a]

This dendron is derived from the first-generation semifluori-

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3331

V. Percec et al.

nated

A

ethyl-3,5-dinitrobenzoic acid (5).^[8a]The commercially avail-

able naphthalic anhydride (6) and 4-nitronaphthalic anhy-

dride (7) were reacted with 2-(2-aminohydroxy)ethanol to

produce imides 9 and 10, respectively, in moderate yields.

DCC/DPTS-mediated esterification of 1 with the hydroxy-

terminated naphthylimide derivatives 9 and 10 produced

glycol spacer between its carboxylic acid and the electron-

acceptor 4,5,7-trinitro-9-fluorenone (TNF) group. Scheme 1

outlines the synthesis of five new dendrons attached to elec-

tron-acceptor molecules based on the dendron 1. The syn-

thesis, which incorporates an aminothienyldioxocyanopyri-

dine (ATOP) moiety at the apex,

A

G

(A1), was achieved by N,N-dimethylcyclohexylcarbodiimide

(DCC)/4-dimethylaminopyridinium-p-toluenesulfonate

(DPTS) mediated esterification of 1 with ATOP^[18]deriva-

tive 2 in 40% yield. In view of the cyanine type p-conjugat-

ed chromophore of ATOP derivatives, dendron A1 is ex-

pected to be of interest for its potential photorefractive

The synthesis of dendron 12, which incorporates a p-ben-

zaldehyde moiety at the apex, was achieved in 82% yield by

the esterification of the known compound 4-[2-(2-hydroxy-

ethoxy)ethoxy]benzaldehyde (11)^[19]with 1 under DCC/DPTS

conditions. The presence of the reactive benzaldehyde group

at the apexof dendron 12 allows facile derivatization with a

variety of functional groups. Thus, dendron 12 served as a

key precursor for the preparation of two new compounds in-

corporating electron-accepting groups. Condensation of 12

with 1,3-indanedione 13 and malononitrile 14 in the pres-

properties.^[18]

(3,4,5)12F8G1-2EODNB (A2) containing the

A

electron-acceptor 3,5-dinitrobenzoate group at the apexwas

synthesized by the esterification of 3,5-dinitrobenzoic acid

(3) with diethylene glycol 4 in the presence of para-toluene-

sulfonic acid (p-TsOH) and subsequent DCC/DPTS mediat-

ed esterification of 1 with the resulting 2-(2-hydroxyethoxy)-

ence of b-alanine produced (3,4,5)12F8G1-2EOIn (A5) and

A

Figure 2. Structures of self-assembling dendrons containing electron-acceptor (n-type) groups and the results of the retrostructural analysis of their supra-

molecular assemblies.

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Supramolecular Chemistry

FULL PAPER

Scheme 1. i) DCC, DPTS, a,a,a-trifluorotoluene, 558C, 12 h; ii) p-TsOH, 1208C, 4 h; iii) THF, 658C, 2 h; iv) b-alanine, THF, reflux.

A

was achieved by reacting A8 with malononitrile in DMF at

258C. The resulting (3,4,5)12F8G1-2EOTNF (A11), which is

AHCTREUNG

a stronger electron-acceptor than A8, was found to be

highly stable under ambient laboratory conditions. However,

as expected, it was found to be unstable on silica gel. There-

fore, it was purified by repeated recrystallization from a

CH₂Cl₂/MeOH 1:1 mixture.

To further evaluate the scope and limitations of this self-

assembly concept, the synthesis of a dendron with the larger

and more rigid perylene bisimide electron-accepting group

at the apexwas performed. Scheme 3 outlines the synthesis

of the asymmetrically dendronized perylene bisimide deriva-

structural modification of the dendron on the self-assembly

process, four new derivatives of the previously reported den-

dron

The synthesis of these compounds is outlined in Scheme 2.

The synthesis of the semifluorinated acid (3,4)12F8G1-

A

CO₂H (17), which incorporates only two semifluorinated

alkyl chains, was achieved by the alkylation of methyl 3,4-di-

hydroxybenzoate 15 with the known^[10a]compound 12-

bromo-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptafluorododecane.

Subsequent saponification of the methyl ester derivative 16

produced 17 in 64% yield. Esterification of 17 with the

known^[8a]2-(2-{2-[(2-hydroxyethoxy)ethyl]ethyl}ethyl(4,5,7-

tive (3,4,5)12F8G1-2EOPBI (A12). The reaction of 3,4,9,10-

G

perylenetetracarboxylic acid dianhydride (PTCAD, 21) with

two equivalents of 1-ethylpropylamine (22) in pyridine in

trinitro-9-fluorenone)-2-carboxylate

(3,4)12F8G1-2EOTNF (A7) in 60% yield. We recently re-

ported the synthesis of (3,4,5)16F8G1-CO₂H (19), in which

(18)

produced

the presence of Zn(OAc)₂produced the symmetrical pery-

G

lene bisimide derivative 23. The partial hydrolysis of the di-

imide derivative 23 to the corresponding unsymmetrical per-

ylene bisimide 24 was performed according to the method

of Kaiser and co-workers.^[20]In the present case, the solid

AHCTREUNG

the dodecyl semifluorinated group was replaced by a hexa-

decyl group.^[8b]The latter was employed in the synthesis of

1

the new dendron

A

isolated after workup was shown by H NMR analysis to be

corporates a longer semifluorinated alkyl chain. The synthe-

sis of the 4,5,7-trinitro-9-fluorenone based dendron, with the

longer tetraethylene glycol spacer (A1) was achieved by the

esterification of 4,5,7-trinitro-9-fluorenone derivative (20)^[8a]

with semifluorinated acid 1. The carbonyl group from A8

was also substituted with a dicyanomethylene group. This

a mixture of both the desired product 24 and the anhydride

21. H NMR spectroscopy indicated a 63:37 ratio of 24/21.

The mixture was used in the next step without purification.

The reaction of the 24:21 mixture with a large excess of 2-

(2-hydroxyethoxy)ethyl amine produced the desired unsym-

metrical perylene bisimide 25 as well as the expected by-

1

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3333

V. Percec et al.

Scheme 2. i) 2 equiv F

N

12 h; iv) DMF, 258C.

product bis-(1-ethylpropyl)perylene-3,4:9,10-tetracarboxyl-

bisimide. The isolation of pure 25 was achieved by chroma-

tographic separation of the mixture on silica gel using

CH₂Cl₂as eluent. The synthesis of the target product A12

was achieved by Mitsunobu esterification of the semifluori-

nated acid 1 with 25 in the presence of PPh₃and diisopropyl

azodicarboxylate (DIAD) in THF at 258C.

fibers according to methods elaborated previously.^[8a,b]The

transition temperatures and the corresponding enthalpy

changes (kcalmol^ꢀ1) were determined by DSC with heating

and cooling rates of 108Cmin^ꢀ1. The assignment of various

phases was done by a combination of XRD and TOPM as

described previously.^[8,21]Table 1 summarizes the transition

temperatures and the corresponding enthalpy changes for

all self-assembling dendrons. All compounds self-assemble

into supramolecular columns that self-organize into various

columnar LCs. Hexagonal columnar p6mm (F_h) lattices pre-

dominate, as shown by the X-ray diffraction studies dis-

cussed below. All dendrons presented in this study contain

Thermal analysis by differential scanning calorimetry

(DSC): All self-assembling compounds were analyzed by a

combination of DSC, thermal optical polarized microscopy

(TOPM) and small- and wide-angle X-ray diffraction

(XRD) experiments carried out on powder and oriented

flexible oligoether spacers except (3,4,5)12F8G1-PrATOP,

A

Scheme 3. i) pyr, Zn(OAc)₂, reflux; ii) 2-methyl-2-propanol, KOH, 100 8C, 30 min. followed by acidification with aq. HCl; iii) DIAD, PPh₃, THF, 238C.

G

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Chem. Eur. J. 2007, 13, 3330 – 3345

Supramolecular Chemistry

FULL PAPER

which incorporates an aliphatic spacer. This dendron exhib-

its a simple rectangular columnar phase p2mm (F_r-s). In ac-

cordance with our previous observation,^[8b]the presence of

the aliphatic spacer enhances the tendency towards self-as-

sembly into columnar structures that self-organize into col-

umnar phases with intracolumnar order or even crystalliza-

tion (F^k_r-s, k = crystalline). In a previous publication,^[8b]it

was reported that the incorporation of a relatively small

moiety, such as a disubstituted phenyl ring at the apexof

the semifluorinated dendron, induces a monotropic behav-

ior. This structural effect was reproduced in the present

its an enantiotropic centered rectangular columnar c2mm

(F_r-c) phase over a temperature range of more than 708C.

Its isotropization temperature is 1218C. Decreasing the

number of semifluorinated alkyl tails from three to two as

in (3,4)12F8G1-2EOTNF leads to a monotropic simple rec-

A

tangular crystal phase (F^k_r-s) and a higher isotropization tem-

perature (1488C). Increasing the proportion of methylene

groups from (CH₂)₄-(CF₂)₈F to (CH₂)₈-(CF₂)₈F, as in

(3,4,5)16F8G1-2EOTNF, mediates the formation of a F_h

phase and leads to a small increase in the isotropization

temperature and the temperature range of the ordered

phase. Increasing the length of the ether spacer from diethy-

lene glycol (2EO) to tetraethylene glycol (4EO), as in

study. Thus, (3,4,5)12F8G1-2EODNB, which incorporates an

A

electron-accepting disubstituted phenyl ring at the apex, ex-

hibits a relatively small LC (F_h) temperature range only

A

after the first heating.

N

F_hphase, but leads to a small decrease in the isotropization

temperature without affecting the LC temperature range. Fi-

nally, substitution of the carbonyl group by a dicyanomethy-

ACHTREUNG

derivatives at the apexas the electron-acceptor groups, ex-

hibit similar F_hand similar glassy (g) phases. Interestingly,

the substitution of the naphthylimide moiety with a nitro

lene group as in (3,4,5)12F8G1-2EOTNFDCM mediates the

G

formation of an enantiotropic F_hphase and generates a

small decrease of the LC temperature range. The as-pre-

pared sample shows a metastable smectic phase (S) only on

the first heating scan. The DSC of the minidendron contain-

group as in

decrease in the LC temperature range relative to that of a

dendron with an unsubstituted naphthylimide

(3,4,5)12F8G1-2EONpI. Moreover, according to variable

temperature XRD experiments discussed below,

A

N

ing the electron-acceptor perlyene bisimide

A

2EOPBI exhibits an enantiotropic centered rectangular col-

io

^r-c

(3,4,5)12F8G1-2EONNpI exhibits slow dynamics for the

umnar phase with intracolumnar order (F ) over a temper-

transition between F_hand F_h^io

(io = intracolumnar order).^[22]

The dendrons

ACHTREUNG

2EOIn and

ACHTREUNG

compound

(3,4,5)12F8G1-PrATOP

(3,4,5)12F8G1-2EODNB

(3,4,5)12F8G1-2EONpI

(3,4,5)12F8G1-2EONNpI

(3,4,5)12F8G1-2EOIn

(3,4,5)12F8G1-2EODCB

(3,4)12F8G1-2EOTNF

thermal transitions [8C] and corresponding enthalpy changes [kcal]^[a]

1st and 2nd heating scans [8C, kcalmol^ꢀ1

]

1st cooling scan [8C, kcalmol^ꢀ1

i 142 (0.36) F^k_r-s95 (2.96) F_r^k_-s

]

2EODCB, which incorporate

substituted p-extended benzyli-

dene electron-accepting moiet-

ies, also self-assemble into

supramolecular columns that

self-organize into F_hphases.

The effects of the structural

modifications of the peripheral

semifluorinated alkyl chain and

the glycolic spacer on the self-

assembly and the self-organiza-

tion processes are demonstrated

by supramolecular structures

N

F^k_r-s75 (2.34) F_r^k_-s146 (10.64) i

F^k_r-s14 (1.44) F_r^k_-s146 (10.64) i

F^k_r-s78 (18.04) i

G

i 57 (0.31) F_h25 (4.15) F_r^k_-s

i 100 (0.41) F_h15 g

F^k_r-s38 (4.85) F_h61.5 (0.29) i

F^k_h48 (4.24) F_h105 (0.34) i

g 19 F_h106 (0.34) i

AHCTREUNG

T

Fⁱ_h^o83 (6.26) F_h115 (0.36) i

Fⁱ_h^o(g) 23 Fⁱ_h^o64 (0.1) F_h115 (0.36) i

F^k_h61 (8.04) F_h111 (0.35) i

g 22 F^k_h64 (6.4) F_h111 (0.34) i

F^k_r-c28 (1.08) F_h79 (0.27) i

F^k_r-c23 (2.14) F_h81 (0.24) i

F^k_r-s148 (13.35) i

i 111 (0.32) F_h79 (0.14) Fⁱ_h^o16

Fⁱ_h^o(g)

i 106 (0.22) F_h29 (1.51) g

G

H

i 77 (0.23) F_h17 (1.31) F_r^k_-c

G

i 143 (0.11) F^k_r-s68.6 (1.23) F^k_r-s

F^k_r-s67 (1.23) F_r^k_-s128.5 (ꢀ11.1)

F^k_r-s148 (13.00) i

self-assembled

(3,4,5)12F8G1-2EOTNF,

(3,4)12F8G1-2EOTNF,

(3,4,5)16F8G1-2EOTNF,

from

G

F^k_r-c50 (2.03) F_r-c121 (0.43) i

g 34 F_r-c121 (0.43) i

i 115 (0.44) F_r-c33 g

ACHTREUNG

AHCTREUNG

F^k_h114 (15.60) F_h125 (0.30) i

F^k_r-c58 (4.75) F_h125 (0.35) i

F^k_r-s48 (2.91) F_h118 (0.33) i

g 23 F_h118 (0.23) i

i 121 (0.31) F_h44 (4.16) F _r^k_-c

i 115 (0.21) F_h14 g

ACHTREUNG

and

AHCTREUNG

A

contain the parent 4,5,7-trini-

tro-9-fluorenone-2-carboxy

R

S 116 (8.04) i

i 104 (0.11) F_h40 g

g 49 F_h114 (0.15) i

io

^r-c

electron-accepting moiety. The

C

F

137 (5.79) F 200 (2.80) i

i 195 (2.71) F 139 (0.12) F_r^k_-c

^r-c

io

previously reported^[8c]dendron

F

149 (0.11) F 200 (2.82) i

r-c

[a] Thermal transitions (8C) and enthalpy changes (kcalmol) were determined by DSC (108Cmin^ꢀ1). Data

from the first heating and cooling scans are on the first line and data from the second heating are on the

second line. F_r-s= p2mm simple rectangular columnar lattice; F^k_r-s= p2mm crystal simple rectangular colum-

nar lattice; F_h= p6mm hexagonal columnar lattice; Fⁱ_h^o= p6mm hexagonal columnar lattice with intracolum-

nar order; F^k_h= p6mm crystal hexagonal columnar lattice; F_r-c= c2mm centered rectangular columnar lat-

A

lected as a reference and its

supramolecular structure was

compared with that of the other

io

tice; F = c2mm centered rectangular columnar lattice with intracolumnar order; F^k_r-c= c2mm crystal cen-

three

^r-c

A

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3335

V. Percec et al.

ature range of 508C. Among all minidendrons investigated

in this study, (3,4,5)12F8G1-2EOPBI exhibits the highest

isotropization temperature at 2008C on the first heating

Structural and retrostructural analysis by X-ray diffraction

(XRD): Figure 2 summarizes the XRD structural analysis of

the dendronized electron-accepting groups. Small-angle

(Table 2) and wide-angle XRD (Table 3) studies indicate

that many of these dendrons self-assemble into columns

which at high temperature self-organize into a 2D hexagonal

columnar LC phase (F_h). This is demonstrated by three

sharp reflections with the indices (10), (11), and (20) in

small-angle powder XRD. The (10) peak is very strong and

the (11) and (20) peaks are weak. The smallest supramolec-

ACHTREUNG

cycle.

Textural studies by thermal optical polarized microscopy

(TOPM): Dendron A2 is discussed as a representative ex-

ample for the thermal optical polarized microscopy studies.

Cooling from isotropic melt (T = 578C) generates many L-

type and fan-shaped dark brushes over most of the visible

field, indicative of the formation of a F_hphase (Figure 3).^[23]

The texture completely changes upon shearing, which re-

flects its liquid crystalline nature. The sample was cooled to

258C, at which there was a strong endothermic peak in the

DSC, and the texture remained unchanged except in color

(Figure 3b). Attempts to move the cover slide at this tem-

perature do not visibly affect the texture (Figure 3c). Re-

heating the sample to 418C also does not affect the texture,

except that it reverts to the original color (Figure 3d). This

texture shears easily (Figure 3e) and slowly anneals to a

physically robust multi-colored needlelike texture (Fig-

ure 3f). The appearance of many sharp rings in both the

wide-angle and small-angle region of the XRD confirm that

the material has crystallized.

ular column diameter was observed for

2EONpI (45.1 ) and the largest was observed for

(3,4,5)12F8G1-4EOTNF (54.5 ) (Table 2). Oriented fibers

A

AHCTREUNG

of many of these dendrons were studied by both small- and

wide-angle XRD. The fibers were extruded from a miniex-

truder in the LC phase, if accessible, cooled to room temper-

ature, and then kept in a temperature-controlled oven for

temperature-dependent XRD measurements. In the well-

oriented fibers, sharp reflections with a large maximum in

intensity near the equator (perpendicular to the extrusion

direction) were observed in the small-angle region in the LC

phase. Figure 4 shows the wide-angle XRD meridional q

plots of oriented fibers of nine dendrons. The p–p stacking

distance ranges from 3.5 to 3.8 , indicating an efficient

face-to-face overlap between adjacent electroactive moieties

at the centers of the supramolecular columns. This efficient

p-overlap and the increased positional order between the

molecular cores (along the column axis) is most likely re-

sponsible for the increase in the charge-carrier mobility

along the column axis.^[8a]This is a requisite for practical ap-

plication of these materials as molecular electronic compo-

nents or photoconductors. The wide-angle XRD results for

seven minidendrons obtained in oriented fibers are summar-

ized in Table 3. The supramolecular columns consist of a

pine-tree or pyramidal helical arrangement of dendrimer-

s.^[8a,b]The tilt angle of the dendron in the pyramidal supra-

molecular dendrimer varies between 63 and 228 and the

short range helical pitch is between 5.1 and 5.4 .

The wide-angle XRD of (3,4,5)12F8G1-2EODNB at 438C

G

in the LC phase shows the appearance of broad X shaped

features located off the fiber axis and subtending ꢁ858 be-

tween them (Figures 5 and 6a). These features are correlat-

ed with the tilt of the molecule in the supramolecular

column. In addition, two pairs of broad spots off-center

from the fiber axis and with a large intensity along the meri-

dional axis were noted, demonstrating short-range helical

order of the molecule (Figure 6a). The existence of helical

order was supported in the case of related supramolecular

structures by circular dichroism experiments.^[22]Long-range

helical order with higher-order X-shaped diffractions was

observed for assemblies with shorter alkyl tails.^[22d]At larger

angles, there is an additional set of two spots centered

nearly on axis. The d spacing corresponding to these spots is

3.6 , indicative of p-electron overlap between molecular

cores along the column axis. At a lower temperature (308C),

below that of the endothermic peak observed in the DSC,

these features become dramatically enhanced and distinct

Figure 3. Textures of the dendron (3,4,5)12F8G1-2EODNB in the differ-

A

ent phases: a) at 568C in the F_hLC phase obtained by cooling from the

isotropic; b) cooling down to 258C; c) after shearing of the cover slide;

d) after heating to the LC phase, 418C ; e) after shearing in the LC

phase, 418C; f) after annealing at 558C, transformed to a crystalline

phase.

3336

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Chem. Eur. J. 2007, 13, 3330 – 3345

Supramolecular Chemistry

FULL PAPER

Table 2. Structural and retrostructural analysis by XRD of supramolecular columns and their corresponding lattices generated from dendrons containing

acceptor groups. Data collected during 1st and 2nd heating and 1st cooling scans.

Compound

(3,4,5)12F8G1-PrATOP

Lattice

T [8C]

d Spacings []

a or (a, b) []

A

F^k_r-s

F_h

F^k_r-s

120

25

43

d₁₀(40.5) d₂₀(20.1) d₀₁(17.5)

d₁₀(46.8) d₂₀(20.1) d₀₁(21.4)

d₁₀(39.3) d₂₀(19.6)

d₁₀(41.6) d₀₁(25.3) d₁₁(21.2) d₂₁(16.7) d₃₀

d₀₂(12.9) d₃₁(12.1) d₂₂(10.8) d₄₀(10.3)

d₂₀(21.7) d₁₁(18.5)

d₁₀(39.1) d₁₁(28.7) d₂₀(19.5)

d₁₀(44.2) d₂₀(22.1) d₂₁

d₄₁(9.5) d₁₀(40.3) d₂₀(45.8)

d₁₀(41.9) d₁₁(25.3) d₂₀(20.5)

d₁₀(43.8) d₁₁(25.2) d₂₀(22.4)

d₁₁(47.6) d₂₀(44.9) d₀₂(27.9) d₂₂(23.7) d₁₃

d₁₀(47.6), d₂₀(23.3) d₀₁(15.7)

d₁₀(47.9), d₀₁(29.9) d₂₀(23.8)

d₁₁(44.3) d₀₂(41.3) d₂₀(25.5) d₂₂(21.8) d₀₄

d₁₀(46.3), d₁₁(26.7) d₂₀(23.1)

40.2, 17.5^[a]

48.0, 21.4^[a]

45.4^[b]

(3,4,5)12F8G1-2EODNB

50

A

42.4, 25.5^[a]

F^k_r-s

F_h

Fⁱ_h^o

25

80

40

93

100

65

15

90

25

90

23

43.4, 20.4^[a]

45.1^[b]

T

N

G

(10.2)

51.1^[b]

F_h

46.2^[b]

N

F_h

48.8^[b]

R

F_h

50.2^[b]

F^k_r-c

F^k_r-s

F_r-c

F_h

(18.3)

90.0, 55.9^[c]

47.6, 15.7^[a]

47.6, 29.9^[a]

82.0; 51.4^[c]

53.5^[b]

A

N

ACHTREUNG

F^k_r-c

d₁₀(46 d₁₁₀(53.2) d₀₂₀

(25.9) d₁₅₀(19.5) d₀₆₀(17.1) d₄₀₀(15.6) d₃₅₀(14.5)

d₀₈₀(13.0) d₃₇₀(12.0) d₆₀₀(10.5)

d₁₀(47.6) d₁₁(27.1) d₂₀(23.5)

(50.3) d₂₀₀

62.5, 102.0^[c]

AHCTREUNG

G

F_h

F^k_r-s

F_h

S

40

20

80

25

180

54.5^[b]

d₁₀(48.7) d₁₁(45.9) d₀₃(39.9) d₁₃(29.9) d₂₀(24.5)

d₁₀(43.6) d₁₁(25.2) d₂₀(21.6)

d₁₀(39.3) d₂₀(19.6)

d₂₀(61.0) d₁₁(44.5) d₄₀(30.2) d₀₂(23.6)

d₂₂(22.1) d₁₃(15.7)

d₂₀(65.3) d₁₁(46.8) d₀₂(25.2) d₂₂(23.4) d₁₃(16.7)

48.9, 119.9^[a]

50.2^[b]

R

39.3^[d]

io

F

H

120.9; 47.5^[c]

^r-c

io

^r-c

F

80

129.5; 50.4^[c]

[a] p2mm = simple rectangular columnar (F_r-s) lattice parameters a and b; a = hd, b = kd; (h0) and (k0) from XRD. [b] p6mm = hexagonal columnar

pﬃﬃﬃ pﬃﬃﬃ pﬃﬃﬃ pﬃﬃﬃ

(F_h) lattice parameter; a = 2hd₁₀₀

i

3; hd₁₀₀i = (d₁₀₀3d₁₀₀4d₂₀₀7d₂₁₀)/4. [c] c2mm = centered rectangular (F_r-c) lattice parameters a and

+

b; a = hd, b = kd; (h0) and (k0) from diffractions. [d] S = smectic lattice parameter (= layer separation) a = (d₁₀+ 2d₂₀+ 3d₃₀+ 4d₄₀)/4.

Table 3. Structural analysis of aligned fibers by wide-angle XRD.

peaks appear in both the small-

angle and wide-angle regions,

confirming that the LC phase

transforms to a three-dimen-

sional crystalline phase that ex-

hibits clear helical layer lines

(Figure 5c).

Compound

Phase

T [8C]

Tilt angle [8]

Short-range

helical

pitch p []

p-stack

distance

[]

A

F^k_r-s

F_h

Fⁱ_h^o

F_h

F_r-c

F_h

28

44

42

40

92

98

67

25

40

3.7

3.5

3.6

3.7

3.6

3.8

43ꢂ9

21ꢂ4

63ꢂ13

10ꢂ5

32ꢂ17

33ꢂ10

42ꢂ7

40ꢂ6

5.2

5.1

5.3

5.5

5.4

5.2

5.3

ACHTREUNG

Variable temperature XRD

experiments were conducted

ACHTREUNG

for

aligned

fibers

of

ACHTREUNG

AHCTREUNG

ACHTREUNG

(Figure 6). These experiments

demonstrate the slow dynamics

of the transition between the

(Figure 5a), but remain broad. Additional broad peaks

appear along the equator, signaling a structural change. Be-

cause the wide-angle features are still broad and there is no

sharp peak in the wide-angle region, the molecular order

along the column axis is still only short-range. The width of

the equatorial peaks also implies that there is only short-

range order of the two-dimensional lattice formed by the

supramolecular columns. However, the dramatic enhance-

ment of the wide-angle features corresponding to the short-

range helical order, molecular tilt, and the p-electron corre-

lation suggests that there is a dramatic reduction of molecu-

lar motion in this phase. This is consistent with the shear re-

sistance observed in the texture in the TOPM. On heating

to the LC phase and annealing at 508C, many sharp new

F_hand Fⁱ_h^ophases. These slow dynamics were attributed to

the presence of the fluorine-rich aliphatic tail at the periph-

ery of the dendron (fluorophobic effect). Both fiber and

powder XRD experiments indicate the formation of a

higher-order intermediate phase. A closer inspection of the

small-angle XRD plots (Figure 6c) reveals that the (11)

peaks of the F_hare observed only in the temperature range

between 55 and 758C. The second-order core–core stacking

features c₂are observed in a similar temperature range as

evident from the wide-angle XRD experiments, and they

confirm a helical crisscross arrangement in the supramolec-

ular column (Figures 6a, d, and e). The formation of the in-

termediate phase with enhanced intracolumnar order with a

larger number of diffraction peaks is observed above the

Chem. Eur. J. 2007, 13, 3330 – 3345

ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

3337

V. Percec et al.

axis of the column. The XRD of the aligned sample is

shown in Figure 7c, and indicates that p–p stacking is along

the equatorial direction but not along the meridional direc-

tion as assigned for the previous columnar phases (see ex-

amples in Figure 6a). A reconstructed molecular model for

the mechanism of this unprecedented self-assembly process

was elaborated based on the XRD results and is shown in

Figure 7. The correlation length of the p–p stacking is esti-

mated from the full width at half-maximum of this feature

(Figure 8) using x = 2p/Dq. The calculated correlation

length of the s feature is 45 , indicating a small number of

stacked perylene bisimide cores. This is in contrast to the

correlation length of the of the p–p stacking observed for

AHCTREUNG

Figure 4. Wide-angle XRD intensity along the meridional axis. Curves

are offset for clarity. The p–p stacking features and d spacings are indi-

cated.

most probably associated with the relatively large size of the

perylene bisimide core relative to other electron-acceptor

cores.

It appears that the use of a low-generation semifluorinat-

ed dendron does not induce p-stacking of relatively volumi-

nous electron-acceptor cores in the center of supramolecular

columns. A possible direction towards overcoming this limi-

tation would be to attach the large electroactive cores to

higher-generation (2nd or 3rd) semifluorinated dendrons.

Alternatively, in the case of perylene bisimide, a symmetri-

cally dendronized core would probably induce p-stacking of

the core in the center of supramolecular columns. The later

direction is currently being pursued and will be reported.

Figure 5. Wide-angle X-ray patterns of oriented fibers of (3,4,5)12F8G1-

A

2EODNB: a) in the disordered crystalline phase at 308C; b) in the 2D

hexagonal columnar LC phase at 438C, and c) in the 3D crystalline phase

at 508C. s = the ꢁ3.5 p–p stacking feature; (10) = the (10) reflection

of the columnar hexagonal phase; m = higher order (hk0) reflections of

the columnar hexagonal phase; l = helical layer lines. The fiber axis is

vertical.

Conclusion

The synthesis and structural and retrostructural analysis of a

library of twelve combinations of three semifluorinated ta-

pered first-generation dendrons or “minidendrons” function-

alized at their apexwith eight different electron-acceptor

groups are reported. These results demonstrate that func-

tional dendrons self-assemble into supramolecular helical

pyramidal columns containing p-stacks of the electron-ac-

ceptor groups that have their long axis perpendicular to the

long axis of the column. The supramolecular columns self-

organize into F_h, F_r-c, and F_r-speriodic arrays that exhibit

liquid-crystalline phases, liquid-crystalline phases with intra-

columnar order, and respectively crystalline phases. An ex-

ception from this structural feature was observed for the

glass transition. Thus, heating above the glass transition

leads to an improvement of the self-assembly and subse-

quent self-organization into the highest-order phase. The

XRD patterns shown in Figure 6a indicate the slow reorgan-

ization of the columns, which is manifested by the change of

the position or intensity of the (hk0), c₁, c₂, I, and t features.

Upon further temperature increase, the boundary between

the hydrogenated and fluorinated parts of the alkyl tails be-

comes more diffuse, and consequently the characteristic (11)

peak and c₂feature for the ordered phase disappear and the

c₁stacking feature becomes weaker, as shown in Figure 6d.

This remarkable behavior is fully reversible and demon-

strates the power of the fluorophobic effect to fine tune the

dynamics of this self-assembly process.

dendron (3,4,5)12F8G1-2EOPBI, which self-assembles into

N

a supramolecular pyramidal column containing unprece-

dented stacks of perylene bisimide cores that have their

long axis parallel to that of the long axis of the column. The

results reported here demonstrate that the concept elaborat-

ed previously^[8a]to assemble electronic materials is compati-

ble with a variety of n-type acceptor molecules of small and

medium size. However, when the size of the acceptor be-

comes equal to or larger than that of PBI the self-assembly

process provided a new supramolecular architecture. The

generality of this new supramolecular architecture is under

As demonstrated above, the structural and retrostructural

analyses of all dendrons show clearly that the electron-ac-

ceptor stacks are in the centers of the supramolecular helical

columns. However, an exception was observed in the case of

the dendron (3,4,5)12F8G1-2EOPBI, which according to the

A

XRD results self-assembles into supramolecular columns

with stacks of perylene bisimide cores parallel to the long

3338

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Chem. Eur. J. 2007, 13, 3330 – 3345

Supramolecular Chemistry

FULL PAPER

Figure 6. Phase transition with slow dynamics due to the fluorophobic effect in (3,4,5)12F8G1-2EONNpI: a) XRD patterns of the aligned sample for the

A

marked temperature sequence; b) column diameter; and c) q plots of the hexagonal phase versus temperature, the dotted rectangle marks the region

where the (11) peak is observed; d) q plot along the meridional axis; e) azimuthal angle Chi plot for the 2p/q = 4 to 5 wide angle region. Remark: re-

ported data are perfectly reversible as a function of temperature. Legend: c₁= 3.5 stacking feature; c₂= 7.0 stacking feature observed only in the

55–758C temperature range; t = dendron tilt angle feature; i = short-range helical feature; (hk0) = hexagonal columnar phase diffraction peaks; q =

scattering vector.

investigation. Thus, the present study as well as the previous

publications on this topic^[8a,b]concluded the scope and the

limitations of this self-assembly strategy when the group at

the apexof the dendron is electron-donor or electron-ac-

ceptor. We anticipate that this simple and versatile strategy

for producing conductive p-stacks of aromatic groups will

lead to new classes of supramolecular materials of interest

for electronic and optoelectronic applications. The self-

repair process of the backfolded structural defects from the

p-stacks of acceptor molecules from the core of supramolec-

ular helical pyramidal columns is mediated by heating the

columnar periodic structure to the isotropic state and by its

subsequent cooling to room temperature. This process

(Figure 1) was demonstrated and reported in a previous

publication.^[8a]The scope, limitations, and the mechanisms

of the co-assembly of electron-donor with electron-acceptor-

functionalized dendrons and polymers will be reported in a

future publication.

Experimental Section

Materials: DCC (99%), 2,3-dihydropyran (97%), a,a,a-trifluorotoluene

(99%), p-toluene sulfonic acid (PTSA) (98%), diethylene glycol (4)

(98%), 3,5-dinitrobenzoic acid (3), 4-nitro-1,8-naphthalic anhydride (7),

malononitrile (14), 1,3-indanedione (13), 3,4,9,10-perylenetetracarboxylic

acid dianhydride (PTCDA, 21, Aldrich), 1-ethylpropylamine (22, Aldrich,

9 7%), pyridine (Fisher, reagent grade), 2-(2-hydroxy-ethoxy)-ethylamine

(8, Aldrich, 98%), Zn(OAc)₂·H₂O (Matheson, Coleman and Boil, re-

G

agent grade), diisopropyl azodicarboxylate (DIAD, 95%) (all from Al-

drich). b-Alanine (98%), 1,8-naphthalic anhydride (6) (Acros), K₂CO₃,

Chem. Eur. J. 2007, 13, 3330 – 3345

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www.chemeurj.org

3339

V. Percec et al.

Figure 7. Self-assembly mechanism of (3,4,5)12F8G1-2EOPBI: a) side view of dendron; b) top view of dendron; c) XRD pattern of aligned sample;

G

d) top view schematic of the layers coupling; e) side view of the layers coupling; f) side view of the supramolecular column. s = 3.5 stacking of the

PBI core parallel to the column axis; f₁= 5.4 average layer thickness correlation features; f₂= 10.4 feature corresponding to the every i+2 layer

registry; (hkl) = reflections of the F_r-cc2mm lattice. Color code: PBI core = green, F = blue, O = red, C = gray, H = white, C of the phenyl ring =

light blue.

DMF (ACS reagent, Fisher Scientific) was dried over CaH₂and distilled

under vacuum. Et₂O, Bu₂O, and THF (ACS reagent, Fisher Scientific)

were dried over sodium/benzophenone and distilled. Et₃N was dried

over

CaH₂.

CH₂Cl₂

was

distilled

from

CaH₂.

3,4,5-

Tris(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecyloxy)-

benzoic acid (1),^[10a]12-bromo-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadeca-

fluoro-n-dodecan, (4,5,7-trinitro-9-fluorenone)-2-carboxylate, and 2-(2-{2-

[(2-hydroxyethoxy)ethyl]ethyl}ethyl

(4,5,7-trinitro-9-fluorenone)-2-car-

boxylate (18) were synthesized according to literature procedures.^{[8a, b]}

The synthesis of 2-[2-(4,5,7-trinitro-9-fluorenone-2-carboxy)-ethoxy]-ethyl

3,4,5-tris(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodec-

an-1-yloxy) benzoate (A8) was described previously.^[10a]All other conven-

tional materials and solvents were commercially available and were used

without further purification.

Techniques: ¹H (500 MHz) and ¹³C (125 MHz) NMR spectra in solution

were recorded on a Bruker DRX-500. Chromatographic purifications

were conducted using 200–400 mesh silica gel obtained from Natland In-

ternational Corporation, Morrisville, NC. Thin-layer chromatography

(TLC) was performed on pre-coated TLC plates (silica gel with F₂₅₄indi-

cator; layer thickness, 200 mm; particle size, 5ꢁ25 mm; pore size, 60 ,

Sigma-Aldrich). Melting points were measured using a uni-melt capillary

melting point apparatus (Arthur H. Thomas Company, Philadelphia,

USA) and are uncorrected. High- pressure liquid chromatography

(HPLC) experiments were performed with a Perkin–Elmer Series 10

GPC equipped with a LC-100 column oven (408C), Nelson Analytical

900 Series integrator data station, and two Polymer Laboratories PL gel

columns of 510²and 10⁴, and THF as eluent at 1 mLmin^ꢀ1. Detection

was by UV absorbance at 254 nm. Thermal transitions were measured on

Figure 8. Comparing the average layer separation feature (noted with f in

Figure 7c) and the correlation length, x = 2p/Dq, of the core stacking

feature (noted with s in Figure 7c) of the

ACHTREUNG

nal columnar phase with the

columnar phase.

ACHTREUNG

KOH, MeOH, EtOH, HCl (Fischer), 10% Pd/C and PdCl₂(97%, Lan-

caster) were used as received. 5-(5-Butylethylamino-thiophen-2-ylmethy-

lene)-1-(3-hydroxy-propyl)-4-methyl-2,6-dioxo-1,2,5,6-tetrahydro-pyri-

dine-3-carbonitrile (2) was synthesized by condensation of N-butyl-N-eth-

ylaminoformylthiophene with 1-methyl-4-propan-1-ol-2,6-dioxo-1,2,3,6-

tetrahydro-3-carbonitrile in Ac₂O according to a literature procedure.^[18]

a

TA Instruments 2920 modulated differential scanning calorimeter

(DSC). In all cases the heating and cooling rates were 108Cmin^ꢀ1. First-

3340

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Chem. Eur. J. 2007, 13, 3330 – 3345

Supramolecular Chemistry

FULL PAPER

order transitions were reported as the maxima or minima of the endo-

thermic and exothermic peaks during the second heating and cooling

scans. X-ray diffraction experiments were performed with Cu_Ka1radiation

from a rotating anode (Nonius FR591) X-ray generator operated at

3.4 kW and a multi-wire area detector (Bruker-Siemens). The Cu radia-

tion was collimated and focused with mirror-monochromator optics. The

X-ray beam path is maintained in low vacuum to reduce the background

scattering from air. Primary analysis of the XRD patterns was accom-

plished using Datasqueeze. Un-oriented powder samples were kept in a

temperature-controlled (ꢂ0.18C) oven. Oriented fibers were obtained by

extruding the material in the liquid-crystalline phase using a mini extrud-

er with a hole diameter of 0.5 or 0.7 mm. An Olympus BX-40 optical po-

larized microscope (100magnification) equipped with a Mettler FP 82

hot stage and a Mettler FP 80 central processor was used to verify ther-

mal transitions and to characterize the anisotropic textures. MALDI-

TOF mass spectra were recorded on a PerSpective Biosystems Voyager

DE using 2-(4-hydroxyphenylazo)-benzoic acid as matrix. Angiotensin I

and des-Arg1-Bradykinin were used as standards. Sample preparation

was as follows: The matrix(10 mg) was dissolved in THF (1 mL). The

sample (10 mg) was also dissolved in 1 mL of THF. The matrixsolution

(50 mL) and the sample solution (10 mL) were mixed. The solution of

AgTFA in THF (10 mL, 1 mgmL^ꢀ1) was added to the mixture. The mix-

ture (5 mL) was loaded on a MALDI plate and dried before insertion

into the vacuum chamber of the MALDI instrument. High-resolution

mass spectra (HRMS) were run by direct sample introduction on a

LCMS (Micromass) platform (electron-spray ionizer, electron energy

70 eV). The elemental analyses (C, H) were performed by M-H-W Labo-

ratories, Phoenix, AZ, USA.

2-{2-[3,5-(Dinitrophenoxycarbonyl]ethoxy}-ethyl 3,4,5-tris(12,12,12,11,11,

10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate

[(3,4,5)12F8G1-2EODNB]: Following the procedure described for

A

0.7 mmol), 5 (200 mg), DCC (500 mg) and DPTS (20 mg) was dissolved

in a,a,a-trifluorotoluene (15 mL) and stirred under N₂at 558C for 12 h.

After cooling to 258C, the salts were filtered and the solution was pre-

cipitated into MeOH. The crude product was purified by flash column

chromatography on silica gel using EtOAc/hexanes 40:60, followed by re-

peated precipitations from CH₂Cl₂into MeOH to yield 0.61 g (48.8%).

Purity (HPLC): 99+ %; R_f= 0.23 (silica gel, EtOAc/hexanes 30:70); ¹H

NMR (500 MHz, CDCl₃, 208C, TMS): d = 9.2 (s, 1H; ArH), 9.0 (s, 2H;

ArH), 7.1 (s, 2H; ArH), 4.61 (t, ³J

³J

(H,H) = 4.7 Hz, 2H; OCH₂), 3.99 (m, 6H; 3OCH₂), 3.88 (m, 4H;

(H,H) = 4.7 Hz, 2H; OCH₂), 4.49 (t,

G

2OCH₂), 2.18 (m, 6H; 3CH₂), 1.85 ppm (m, 12H; 6CH₂); ¹³C NMR

(125 MHz, CDCl₃, 208C, TMS): d = 166.2, 162.9, 152.8, 148.7, 133.7,

129.6, 125.3, 122.8, 120.5–108.2 (several CF multiplets), 108.3, 73.0. 69.4,

68.9, 68.8, 65.7, 64.0, 30.8 (t, J(C,F) = 22 Hz), 29.9, 28.9, 17.5, 17.3 ppm;

E

MS (MALDI-TOF): m/z: calcd for C₅₄H₃₇F₅₁N₂O₁₁: 1698.2; found:

1697.45 [M⁺].

2-(2-Hydroxyethoxy)ethyl naphthyl-1,8-imide (9): Compound

6 (2 g,

10 mmol) and 2-(aminoethoxy)ethanol 8 (1.06 g, 10 mmol) were added to

a round-bottom flask containing THF (50 mL)and the mixture was re-

fluxed for 3 h. The reaction mixture was cooled to room temperature and

the solvent was fully evaporated. The resulting residue was dissolved in

minimal amount of MeOH and poured into water. The product was fil-

tered, washed with water, and dried to yield 1.7 g (60%). Purity (HPLC):

1

99+ %; m.p. 1248C; R_f= 0.18 (silica gel, EtOAc/hexanes 6:4); H NMR

(500 MHz, CDCl₃, 208C, TMS): d = 8.62 (m, 2H; ArH), 8.23 (m, 2H;

3-[5-Cyano-3-(5-butylethylamino-thiophen-2-ylmethylene)-4-methyl-2,6-

dioxo-3,6-dihydro-2H-pyridin-1-yl]-propyl-3,4,5tris(12,12,12,11,11,10,10,

ArH), 7.76 (m, 2H; ArH), 4.47 (t, ³J

A

3

(t, J

A

9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)

benzoate

1H; OH); ¹³C NMR (125 MHz, CDCl₃, 208C, TMS): d = 164.9, 134.5,

131.9, 131.8, 128.6, 127.4, 122.9, 72.7, 68.9, 62.2, 39.9 ppm; MS: m/z: calcd

for C₁₆H₁₅NO₄: 285.10; found: 286.11 [M+H⁺].

[(3,4,5)12F8G1-PrATOP]: A mixture of 1 (0.6 g, 0.38 mmol), 2 (0.15 g,

0.38 mmol), DCC (230 mg), and DPTS (10 mg) was dissolved in a,a,a-tri-

fluorotoluene (10 mL) under N₂and stirred for 48 h at 558C. The mixture

was cooled to 258C, salts were filtered, and the solution precipitated into

MeOH. The crude product was further purified by flash column chroma-

tography on silica gel using EtOAc/hexanes 50:50. The solvent was

evaporated and the product was repeatedly precipitated from CH₂Cl₂

into MeOH to yield 0.3 g (40.3%). Purity (HPLC): 99+ %; R_f= 0.23

(silica gel, EtOAc/hexanes 50:50); ¹H NMR (500 MHz, CDCl₃, 208C,

TMS): d = 7.51 (s, 2H; ArH), 7.33 (s, 2H; ArH), 6.40 (m, 1H; CH), 4.37

(m, 2H; NCH₂), 4.21 (m, 2H; NCH₂), 4.05 (m, 6H; 3OCH₂), 3.60 (m,

2H; NCH₂), 3.51 (m, 2H; OCH₂), 2.46 (s, 3H; NCH₂CH₂), 2.18–2.13 (m,

6H; 3CH₂), 2.1–1.8 (m, 16H; overlap 8CH₂), 1.45 (m, 2H; CH₂), 1.35

(m, 3H; CH₃), 1.00 ppm (m, 3H; CH₃); ¹³C NMR (125 MHz, CDCl₃,

208C, TMS): d = 175.8, 166.5, 163.5, 162.4, 152.8, 152.5, 142.4, 141.9,

129.1, 126.0, 124.7, 117.4, 110.7, 108.3, 90.0, 72.9, 68.8, 63.6, 37.3, 30.8 (t,

2-(2-Hydroxyethoxy)ethyl 4-nitronaphthyl-1,8-imide (10): 4-Nitronaph-

thalic-1,8-anhydride 6 (1.5 g, 6.17 mmol) and 8 (0.65 g, 6.17 mmol) were

added to a round-bottom flask containing of THF (50 mL). The reaction

mixture was refluxed for 3 h and then was cooled to room temperature.

The solvent was evaporated and the resulting residue was dissolved in a

minimum amount of MeOH and poured into water. The product was fil-

tered, washed with water, and dried to yield: 1.7 g (60%). Purity

(HPLC): 99+ %; R_f= 0.21 (silica gel, Et₂O); m.p. 1018C; ¹H NMR

(500 MHz, CDCl₃, 208C, TMS): d = 8.84 (m, 1H; ArH), 8.75 (m, 1H;

ArH), 8.70 (m, 1H; ArH), 8.40 (m, 1H; ArH), 8.00 (m, 1H; ArH), 4.46

(t, ³J

(H,H) = 4.7 Hz, 2H; NCH₂), 3.88 (m, 2H; OCH₂), 3.67 (m, 4H;

C

2OCH₂), 2.25 ppm (brs, 1H; OH); ¹³C NMR (125 MHz, CDCl₃, 208C,

TMS): d = 164.0, 163.2, 150.1, 133.0, 130.4, 130.3, 129.9, 129.6, 127.2,

124.3, 124.1, 123.3, 72.7, 68.6, 62.2, 40.3 ppm; MS: m/z: calcd for

C₁₆H₁₄N₂O₆: 330.09; found 353.07 [M+Na⁺].

J(C,F) = 22 Hz), 29.9, 28.9, 20.4, 19.1, 17.7, 17.5, 17.3, 14.0, 12.6 ppm;

A

MS (MALDI-TOF): m/z: calcd for C₆₄H₅₂F₅₁N₃O₇S: 1975.2; found:

1998.8 [s+Na⁺].

2-[2-(Naphthyl-1,8-imido)ethoxy]ethyl 3,4,5-tris(12,12,12,11,11,10,10,9,9,

8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)benzoate [(3,4,5)12F8G1-

2-(2-Hydroxyethoxy)ethyl 3,5-dinitrobenzoate (5): Compound 3; 10 g,

47.2 mmol) and p-toluenesulfonic acid (0.5 g) were added to a round-

bottom flask containing 4 (25 mL). The mixture was stirred at 1208C for

4 h. The reaction mixture was cooled to room temperature and poured

into water (400 mL). The resulting precipitate was filtered off and dried.

The crude product was purified by column chromatography (silica gel)

using hexanes/EtOAc 3:7. The fractions containing the product were col-

lected and the solvents were evaporated to produce a crude product. Re-

crystallization of the crude product from 2-propanol gave the pure prod-

uct as pale yellow crystals (7.86 g, 56%). Purity (HPLC): 99+ %; m.p.

888C; R_f= 0.11 (silica gel, EtOAc/hexanes 4:6); ¹H NMR (500 MHz,

CDCl₃, 208C, TMS): d = 9.23 (s, 1H; ArH), 9.19 (s, 2H; ArH), 4.63 (t,

2EONpI]: Following the procedure described for (3,4,5)12F8G1-

A

PrATOP, a mixture of 1 (0.3 g, 0.19 mmol), compound 9 (50 mg), DCC

(120 mg), and DPTS (0.2 mg) was dissolved in a,a,a-trifluorotoluene

(5 mL) and stirred under N₂at 558C for 16 h. After cooling to 258C, the

salts were filtered and the solution precipitated into MeOH. The crude

product was precipitated five times from CH₂Cl₂into MeOH, then dried

in a vacuum oven at 258C for 24 h to yield 0.22 g (63%). Purity (HPLC):

99+ %; R_f

(500 MHz, CDCl₃, 208C, TMS): d = 8.51 (m, 2H; ArH), 8.18 (m, 2H;

=

0.66 (silica gel, EtOAc/hexanes 40:60); ¹H NMR

3

ArH), 7.71 (m, 2H; ArH), 7.20 (s, 2H; ArH), 4.45 (t, J(H,H) = 4.7 Hz,

A

2H; NCH₂), 4.03 (m, 6H; 3OCH₂), 3.88 (m, 4H; 2OCH₂), 2.15 (m, 6H;

3CH₂), 1.87 ppm (m, 12H; 6CH₂); ¹³C NMR (125 MHz, CDCl₃, 208C,

TMS): d = 166.2, 164.6, 152.8, 142.1, 134.3, 132.0, 131.6, 128.6, 127.3,

125.7, 122.9, 120.5–108.2 (several CF multiplets), 108.5, 73.0. 69.1, 68.8,

³J

A

ACHTREUNG

3.79 (m, 2H; OCH₂), 3.68 (t, ³J

AHCTREUNG

(brs, 1H; OH); ¹³C NMR (125 MHz, CDCl₃, 208C, TMS): d = 166.6,

148.6, 129.5, 122.5, 72.5, 68.7, 65.6, 61.7 ppm; MS: m/z: calcd for

C₁₁H₁₂N₂O₈: 300.06; found 323.04 [M+Na⁺].

68.4, 64.7, 39.4, 30.8 (t, J(C,F) = 22 Hz), 30.1, 29.1, 17.5, 17.3 ppm; MS

R

(MALDI-TOF): m/z: calcd for C₅₉H₄₀F₅₁NO₈: 1859.19; found: 1883.8

[M+Na⁺], 1899.82 [M+K⁺].

Chem. Eur. J. 2007, 13, 3330 – 3345

ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

3341

V. Percec et al.

2-[2-(4-Nitronaphthyl-1,8-imido)ethoxy]ethyl 3,4,5-tris(12,12,12,11,11,10,

10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)benzoate

[(3,4,5)12F8G1-2EONNpI]: Following the procedure described for

tion mixture was cooled to room temperature and solvent was removed

under vacuum. The resulting solid was suspended in MeOH (10 mL), fil-

tered, washed with water and MeOH, and dried. Recrystallization from

CH₂Cl₂/MeOH 1:1 gave a pale yellow powder (0.50 g, 97%). Purity

(HPLC): 99+ %;

A

DCC (160 mg), and DPTS (0.2 mg) was dissolved in a,a,a-trifluoroto-

luene (5 mL) and stirred under N₂at 558C for 16 h. After cooling to

258C, the salts were filtered and the product was precipitated by the ad-

dition of MeOH. The crude product was purified by flash column chro-

matography on silica gel using EtOAc/hexanes 40:60, followed by repeat-

ed precipitations from CH₂Cl₂into MeOH to yield 0.31 g (65.1%). Purity

(HPLC): 99+ %; R_f= 0.44 (silica gel, EtOAc/hexanes 40:60); ¹H NMR

(500 MHz, CDCl₃, 208C, TMS): d = 8.82 (m, 1H; ArH), 8.63 (m, 1H;

ArH), 8.55 (m, 1H; ArH), 7.92 (m, 1H; ArH), 7.14 (m, 2H; ArH), 4.45

R_f= 0.67 (silica gel, CH₂Cl₂/EtOAc 3:1); ¹H NMR (500 MHz, CDCl₃,

208C, TMS): d = 7.87 (d, J = 10 Hz, 2H; ArH), (s, 1H, ArH), 7.61 (s,

1H; ArH), 7.25 (s, 2H; ArH), 7.01 (d, J = 10 Hz, 2H; ArH), 4.58 (t, J =

4.95 Hz, 2H; ArH), 4.23 (q, J = 5 Hz, 2H; ArH), 4.06–4.01 (m, 6H;

3OCH₂), 3.92–3.80 (m, 4H; 2OCH₂), 2.20–2.12 (m, 6H, 3CH₂), 1.96–

1.82 ppm (m, 12H; 6CH₂); ¹³C NMR (125 MHz, CDCl₃, 208C, TMS):

d = 166.4, 164.1, 159.0, 152.9, 133.7, 125.9, 115.9, 114.6, 113.6, 108.7, 79.3,

73.1, 69.9, 69.7, 68.9, 68.9, 68.4, 64.2, 31.0–30.1, 29.15, 17.7 ppm; MS

(MALDI-TOF): m/z: calcd for C₅₇H₃₉F₅₁N₂O₇: 1832.2; found: 1831.4

[M⁺], 1870.9 [M+K⁺].

(t, ³J

3OCH₂), 3.87 (m, 4H; 2OCH₂), 2.16 (m, 6H; 3CH₂), 1.89 ppm (m, 12H;

6CH₂); ¹³C NMR (125 MHz, CDCl₃, 208C, TMS): d

166.3, 163.8,

A

=

Methyl 3,4-bis(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-

dodecan-1-yloxy)benzoate [(3,4)12F8G1-CO₂Me] (16): In a three-neck

round-bottom flask equipped with a condenser, Ar inlet-outlet, and a

magnetic stirrer, a mixture of K₂CO₃(5 g, 4 equiv) and DMF (80 mL)

was bubbled with Ar for 0.5 h to eliminate air. Methyl 3,4-dihydroxyben-

zoate (15) (0.6 g, 3.58 mmol) was added and the mixture was heated to

808C. 2-Bromo-1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-n-dodec-

ane (3.98 g, 7.16 mmol) was added and the mixture was stirred under Ar

atmosphere at 808C for 12 h. TLC analysis showed complete reaction.

The reaction mixture was cooled to room temperature and poured into

water (100 mL). The product was extracted with diethyl ether (2

100 mL). The combined organic solution was washed successively with

water, aq. HCl 10%, saturated NaHCO₃, and brine. The organic solution

was dried over MgSO₄and the ether was evaporated. The resulting crude

product was recrystallized from acetone to give 16 as white crystals

(3.5 g, 88%). Purity (HPLC): 99+ %; R_f= 0.47 (EtOAc/hexanes 1:4);

m.p. 878C; ¹H NMR (500 MHz, CDCl₃, 208C, TMS): d = 7.67 (d, J =

10 Hz, 1H; ArH), 7.55 (s, 1H; ArH), 6.87 (d, J = 10 Hz, 1H; ArH), 4.10

162.9, 152.8, 149.9, 142.2, 132.8, 130.2, 129.7, 129.5, 127.1, 125.5, 124.2,

124.0, 123.2, 120.5–108.2 (several CF multiplets), 108.4, 73.0. 69.1, 68.8,

68.2, 64.4, 39.4, 30.8 (t, J(C,F) = 22 Hz), 30.1, 29.1, 17.5, 17.3 ppm; MS

R

(MALDI-TOF): m/z: calcd for C₅₉H₃₉F₅₁N₂O₁₀: 1904.1; found: 1929.2

[M+Na⁺], 1944.8 [M+K⁺].

2-(2-[4-Formylphenyl]ethoxy)ethyl 3,4,5-tris(12,12,12,11,11,10,10,9,9,8,8,

7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)benzoate (12): A mixture

containing 4-[2-(2-hydroxyethoxy)ethoxy]benzaldehyde (11; 0.16 g,

0.76 mmol), 1 (1.0 g, 0.63 mmol), DCC (0.25 g, 1.21 mmol), DPTS (40 g,

0.13 mmol), and a,a,a-trifluorotoluene (10 mL) was stirred at 508C

under Ar for 24 h. The reaction mixture was filtered and washed with

CH₂Cl₂. The filtrate solution was concentrated under vacuum and the

crude product was precipitated by the addition of MeOH. The crude

product was purified by silica gel column chromatography using CH₂Cl₂/

EtOAc 3:1 to give 12 as a white powder (0.92 g, 82%). Purity (HPLC):

99+ %; R_f= 0.73 (silica gel, CH₂Cl₂/EtOAc 3:1); ¹H NMR (500 MHz,

CDCl₃, 208C, TMS): d = 9.87 (s, 1H), 7.81 (dd, J = 8.75, 2.65 Hz, 2H;

ArH), 7.28 (s, 2H; ArH), 6.99 (dd, J = 8.75, 2.65 Hz, 2H; ArH), 4.51 (t,

(t, J

= 5.7 Hz, 4H; 2OCH₂), 3.89 (s, 3H; OCH₃), 2.2–2.1 (m, 4H,

³J

A

2CH₂), 1.95–1.85 ppm (m, 8H; 4CH₂); ¹³C NMR (125 MHz, CDCl₃,

208C, TMS): d = 167.3, 153.1, 148.6, 124.2, 123.2, 114.3, 112.1, 120.5–

4.01 (m, 6H; 2OCH₂), 3.92–3.89 (m, 4H; 2OCH₂), 2.19–2.12 (m, 6H;

3CH₂), 1.91–1.83 ppm (m, 12H; 6CH₂); ¹³C NMR (125 MHz, CDCl₃,

208C, TMS): d = 191.0, 166.48, 164.1, 153.6, 152.9, 142.4, 132.3, 130.6,

125.5, 118.7, 116.3, 115.2, 111.4, 111.2, 108.7, 105.9, 69.9, 68.8, 68.2, 64.3,

32.7, 31.3, 31.2, 31.0, 29.1, 29.0, 26.6, 17.7, 17.5 ppm; MS (MALDI-TOF):

m/z: calcd for C₅₄H₃₉F₅₁O₈: 1784.1; found: 1807.2 [M+Na⁺].

108.2 (several CF multiplets), 68.8, 68.6, 52.4, 30.6 (t, J(C,F) = 22 Hz),

G

30.1, 29.1, 17.7 ppm; elemental analysis calcd (%) for C₃₂H₂₂F₃₄O₄: C

34.43, H 1.99; found C 34.50, H 1.74.

3,4-Bis(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-

1-yloxy)benzoic acid [(3,4)12F8G1-CO₂H] (17): KOH solution (5 mL

20%) was added to a solution of 1 (3.5 g, 3.14 mmol) in EtOH (50 mL).

The mixture was refluxed for 4 h. TLC analysis showed complete reac-

tion. The solvent was evaporated and the resulting potassium salt was

dissolved in THF/H₂O 3:1 (50 mL). The solution was acidified with 2m

HCl until pH 4. Water (50 mL) was added and the product was filtered,

washed with water and methanol, and dried. Recrystallization from ace-

2-(2-[4-{1,3-Dioxoindan-2-ylidenemethyl}phenyl]ethoxy)ethyl

tris(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-

yloxy)benzoate [(3,4,5)12F8G1-2EOIn]: mixture of compound 12

3,4,5-

A

(0.5 g, 0.28 mmol), 1,3-indanedione (13; 0.06 g, 0.41 mmol), and b-alanine

(0.01 g, 0.11 mmol) in dry THF (15 mL) was heated at refluxfor 2 d. The

reaction mixture was cooled to room temperature and the solvent was re-

moved under vacuum. The resulting solid was precipitated in 10 mL of

MeOH, filtered, washed with water and MeOH, and dried. Recrystalliza-

tion from CH₂Cl₂/MeOH 1:1 gave the title compound as a yellow powder

(0.48 g, 90%). Purity (HPLC): 99+ %; R_f= 0.57 (silica gel, CH₂Cl₂/

EtOAc 3:1); ¹H NMR (500 MHz, CDCl₃, 208C, TMS): d = 8.56 (d, J =

8.9 Hz, 2H; ArH), 8.02 (dd, J = 8.62, 3.11 Hz, 2H; ArH), 8.02 (s, 1H;

ArH), 7.83 (dd, J = 8.62, 3.11 Hz, 2H; ArH), 7.31 (s, 1H; ArH), 7.04 (d,

J = 8.9 Hz, 2H; ArH), 4.45 (t, J = 4.88 Hz, 2H; CH₂), 4.29 (q, J =

5 Hz, 2H; CH₂), 4.09–4.03 (m, 6H; 3OCH₂), 3.96–3.88 (m, 4H; 2OCH₂),

2.24–2.12 (m, 6H; 3CH₂), 1.96–1.84 ppm (m, 12H; 6CH₂); ¹³C NMR

(125 MHz, CDCl₃, 208C, TMS): d = 191.1, 189.9, 166.5, 163.5, 152.9,

146.9, 142.8, 142.4, 140.4, 137.5, 135.4, 135.3, 127.19, 127.12, 125.5, 123.5,

123.4, 118.7–118.6 (m), 116.3, 115.26, 111.4–110.6 (m), 108.9, 108.6, 73.0,

69.9, 69.8, 68.88, 68.2, 64.4, 31.2–31.0, 30.85, 29.15, 117.7–117.5 ppm; MS

(MALDI-TOF): m/z: calcd for C₆₃H₄₃F₅₁O₉: 1912.2; found: 1935.2

[M+Na⁺], 1952.74 [M+K⁺].

tone produced white crystals (2.2 g, 64%). Purity (HPLC): 99+ %; R_f

=

0.77 (EtOAc/hexanes 1:1); m.p. 1398C; ¹H NMR (500 MHz, CDCl₃,

208C, TMS): d = 7.72 (d, J = 10 Hz, 1H; ArH), 7.55 (s, 1H; ArH), 6.88

(d, J

= 10 Hz, 1H; ArH), 4.10 (brs, 4H; 2OCH₂), 2.2–2.1 (m, 4H;

2CH₂), 1.95–1.85 ppm (m, 8H; 4CH₂); ¹³C NMR (125 MHz, CDCl₃,

208C, TMS): d = 171.0, 153.6, 147.9, 123.7, 123.3, 114.9, 111.0, 120.5–

108.2 (several CF multiplets), 68.9, 68.6, 30.8 (t, J(C,F) = 22 Hz), 30.1,

G

29.0, 17.7 ppm; elemental analysis calcd (%) for C₃₁H₂₀F₃₄O₄: C 33.77, H

1.83; found: C 33.77, H 1.83.

2-[2-(4,5,7-Trinitro-9-fluorenone-2-carboxy)ethoxy]ethyl 3,4-tris(12,12,12,

11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)benzoate

[(3,4)12F8G1-2EOTNF]: A mixture containing 17 (0.5 g, 0.45 mmol) and

18 (0.21 g, 0.45 mmol) was dissolved in a,a,a-trifluorotoluene (15 mL)

under N₂. DCC (0.28 g, 1.88 mmol) and DPTS (9 mg, 0.03 mmol) were

added and the reaction mixture was stirred at 558C for 72 h under N₂.

The progress of the reaction was monitored by TLC. The solution was

concentrated and the product was precipitated by the addition of MeOH.

Purification of the crude product was performed by column chromatogra-

phy (silica gel, EtOAc/hexanes 1:1), followed by precipitation from

CH₂Cl₂solution by the addition of MeOH to yield reddish crystals

(0.42 g, 60%). Purity (HPLC): 99+ %; R_f= 0.41 (silica gel, EtOAc/hex-

2-(2-[4-{2,2-Dicyanovinyl}phenyl]ethoxy)ethyl

10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)benzoate

[(3,4,5)12F8G1-2EODCB]: mixture of compound 12 (0.5 g,

3,4,5-tris(12,12,12,11,11,

A

0.28 mmol), malononitrile 14 (0.03 g, 0.45 mmol), and b-alanine (0.01 g,

0.11 mmol) in dry THF (15 mL) was heated at refluxfor 4 d. The reac-

3342

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ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eur. J. 2007, 13, 3330 – 3345

Supramolecular Chemistry

FULL PAPER

anes 1:1); ¹H NMR (500 MHz, CDCl₃, 208C, TMS): d = 9.00 (s, 1H;

ArH), 8.82 (s, 1H; ArH), 8.75 (s, 1H; ArH), 8.65 (s, 1H; ArH), 7.72 (d,

J = 8.4 Hz, 1H; ArH), 7.55 (s, 1H; ArH), 6.88 (d, J = 8.3 Hz, 1H;

ArH), 4.62 (t, J = 4.6 Hz, NCH₂), 4.46 (t, J = 4.8 Hz, 2H; OCH₂), 4.01

(t, J = 4.6 Hz, 4H; 2OCH₂), 3.88 (t, J = 4.8 Hz, 4H; 2OCH₂), 2.2–2.1

(m, 4H; 2CH₂), 1.95–1.85 ppm (m, 8H, 4CH₂); ¹³C NMR (125 MHz,

CDCl₃, 208C, TMS): d = 185.2, 166.5, 163.0, 153.2, 149.9, 148.5, 138.9,

138.7, 137.9, 136.5, 135.7, 132.0, 129.6, 125.7, 124.2, 122.9, 122.8, 114.5,

112.1, 120.5–108.2 (several CF multiplets), 69.7, 69.0, 68.9, 68.6, 65.8,

NCH₂), 4.44–4.40 (t,

J

=

3.9 Hz, 2H; OCH₂), 3.90–3.84 (m, 8H;

4OCH₂), 3.78–3.75 (m, 2H; OCH₂), 2.18–2.04 (m, 6H; 3CH₂), 1.84–

1.68 ppm (m, 12H; 6CH₂); ¹³C NMR (125 MHz, CDCl₃, 208C, TMS): d

= 165.6, 162.5, 152.4, 152.3, 149.0, 147.0, 146.7, 141.1, 138.8, 137.7, 135.3,

134.6, 132.9, 130.3, 130.0, 125.9, 124.4, 124.3, 111.9, 111.8, 107.8, 83.8,

73.1, 69.3, 68.5, 68.4, 65.3, 63.8, 30.9–30.8, 29.9, 28.8, 17.3–17.2 ppm; MS

(MALDI-TOF): m/z: calcd for C₆₄H₃₈F₅₁N₅O₁₄: 2069.16; found: 2092.14

[M+Na⁺].

2,9-Bis(1-ethylpropyl)-anthra[2,1,9-def:6,5,10-d’e’f’]diisoquinoline-

64.0, 30.8 (t, J(C,F) = 22 Hz), 30.1, 29.0, 17.7 ppm; elemental analysis

A

1,3,8,10(2H,9H)tetraone (23): A sample of 3,4,9,10-perylenetetracarbox-

C

calcd (%) for C₅₁H₃₉F₅₁N₃O₁₄: C 39.17, H 2.51; found: C 39.17; H 2.51.

ylic acid dianhydride (PTCDA, 21, 14.99 g, 38.21 mmol), zinc acetate di-

hydrate (15.00 g, 68.34 mmol) and 1-ethylpropylamine (22; 10.0 mL,

85.81 mmol) were suspended in pyridine in a reactor fitted with a CaCl₂

drying tube. This was heated to 808C for 2.5 h, then refluxed overnight.

The reaction mixture was precipitated in water and filtered. The crude

product was triturated in 3.5% aq. KOH, to dissolve carboxylic acid

functionalized precursors and intermediates, and filtered. This was re-

peated, and the solid product 23 was triturated in 10% aq. HCl (300 mL)

to remove zinc salts, filtered, then dried overnight at 1058C in a vacuum

oven (11.10 g, 20.92 mmol, 54.75%). The basic filtrates were combined

and acidified with 10% aq. HCl to recover PTCDA (6.16 g, 41.08%) and

uncharacterized CH₂Cl₂soluble components (0.55 g). Purity (HPLC):

2-[2-(4,5,7-Trinitro-9-fluorenone-2-carboxy)ethoxy]ethyl 3,4,5-tris(16,16,

16,15,15,14,14,13,13,12,12,11,11,10,10,9,9-heptadecafluoro-n-hexadec-1-

yloxy)benzoate [(3,4,5)16F8G1-2EOTNF]:

A mixture containing 19

(0.6 g, 0.34 mmol) and 18 (0.15 g, 0.34 mmol) was dissolved in a,a,a-tri-

fluorotoluene (15 mL) under N₂. DCC (0.21 g, 2.06 mmol) and DPTS

(9 mg, 0.03 mmol) were added and the reaction mixture was stirred at

558C for 72 h under N₂. The progress of the reaction was monitored by

TLC. The organic solution was concentrated and precipitated in MeOH

four times from CH₂Cl₂solution. Purification of the crude product was

performed by column chromatography (silica gel, EtOAc/hexanes 1:1),

followed by precipitation into MeOH from CH₂Cl₂solution to yield

orange crystals (0.24 g, 32%). Purity (HPLC): 99+ %; R_f= 0.24 (silica

gel, EtOAc/hexanes 3:7); ¹H NMR (500 MHz, CDCl₃, 208C, TMS): d =

9.00 (s, 1H; ArH), 8.82 (s, 1H; ArH), 8.75 (s, 1H; ArH), 8.65 (s, 1H;

ArH), 7.29 (s, 1H; ArH), 4.62 (t, J = 4.6 Hz, 2H; NCH₂), 4.46 (t, J =

4.8 Hz, 2H, OCH₂), 3.93–3.83 (m, 10H; overlapped 5OCH₂), 2.04 (m,

6H; 3CH₂), 1.77 (m, 2H; CH₂), 1.62 (m, 6H; 3CH₂), 1.53 (m, 6H;

3CH₂), 1.40 ppm (m, 18H; overlapped 9CH₂); ¹³C NMR (125 MHz,

CDCl₃, 208C, TMS): d = 185.2, 166.5, 163.0, 153.2, 149.9, 146,7, 146.5,

140.4, 138.7, 137.9, 135.7, 132.0, 129.6, 125.7, 125.1, 122.9, 120.5–108.2

99+ %; ¹H NMR (500 MHz, CDCl₃, 208C, TMS): d = 8.68 (d, J

8.03 Hz, 4H; ArH), 8.63 (d, J 8.03 Hz, 4H; ArH), 5.07 (m, 2H;

2NCH), 2.23–2.28 (m, 4H; 2CH₂), 1.92–1.98 (m, 4H; 2CH₂), 0.93 ppm

(t, 12H; 4CH₃); ¹³C NMR (125 MHz, CDCl₃, 208C, TMS): d = 11.21,

27.44, 49.35, 121.40, 122.13, 125.22, 128.50, 130.50, 131.1, 165.5 ppm.

=

9-(1-Ethylpropyl)-1H-2-Benzopyrano[6’,5’,4’:10,5,6]anthra[2,1,9-def]iso-

quinoline-1,3,8,10(9H)tetraone (24): This compound was prepared ac-

cording to the method of Kaiser and co-workers.^[20]Compound 23

(11.10 g, 20.92 mmol) was suspended in 2-methyl-2-propanol (150 mL)

and KOH pellets (85%, 3.81 g, 57.72 mmol) were added. This was im-

mersed in a 1008C oil bath for 30 min, then cooled and acidified with

10% aq. HCl. The crude product was recovered by filtration, was sus-

pended in 3.5% KOH (approx250 mL) and filtered. The solid was rinsed

with additional KOH solution (approx250 mL) and then water until the

filtrate was nearly colorless. This unreacted starting material (5.73 g,

10.80 mmol, 51.62%) was dried at 1058C overnight under vacuum. The

filtrate was acidified and filtered to recover 2.85 g of solid rich in the de-

sired product. ¹H NMR (KOH/D₂O) indicated a 63:37 ratio of 24:21.

This was used without further purification. 24: ¹H NMR (in mixture,

approx3.5% KOH/D ₂O, HOD internal standard = 4.67 ppm) d = 7.15

(br, 2H; ArH), 6.87 (br, 2H; ArH), 6.72 (br, 2H; ArH), 6.30 (br, 2H;

(several CF multiplets), 108.0, 73.8, 69.4, 30.6 (t, J(C,F) = 22 Hz), 30.1,

G

29.71, 29.66, 29.61, 29.5, 26.4, 20.5 ppm; elemental analysis calcd (%) for

C₇₆H₇₂F₅₁N₃O₁₅: C 40.82, H 3.25; found: C 40.82, H 3.25.

2-(2-{2-[2-(4,5,7-Trinitro-9-fluorenone-2-carboxy)ethoxy]ethoxy}ethoxy)-

ethyl 3,4,5-tris(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-

dodecan-1-yloxy)benzoate [(3,4,5)12F8G1-4EOTNF]: A mixture contain-

ing 1 (0.54 g, 3.34 mmol) and 20 (0.18 g, 0.34 mmol) was dissolved in

a,a,a-trifluorotoluene (15 mL) under N₂. DCC (0.21 g, 2.06 mmol) and

DPTS (9 mg, 0.03 mmol) were added and the reaction mixture was stir-

red at 558C for 72 h under N₂. The progress of the reaction was moni-

tored by TLC. The solution was concentrated and precipitated in MeOH

four times from CH₂Cl₂solution. Purification of the crude product was

performed by column chromatography (silica gel, EtOAc/hexanes 1:1),

followed by precipitation into MeOH from CH₂Cl₂solution to yield

orange crystals (0.25 g, 36%). Purity (HPLC): 99+ %; R_f= 0.29 (silica

gel, EtOAc/hexanes 2:3); ¹H NMR (500 MHz, CDCl₃, 208C, TMS): d =

9.00 (s, 1H; ArH), 8.82 (s, 1H; ArH), 8.75 (s, 1H; ArH), 8.65 (s, 1H;

ArH), 7.16 (s, 1H; ArH), 4.57 (t, J = 4.6 Hz, 2H; NCH₂), 4.35 (t, J =

5.00 Hz, 2H; 2OCH₂), 4.03 (t, J = 5.8 Hz, 4H; 2OCH₂), 3.96 (m, J =

5.8 Hz, 2H; OCH₂), 3.87 (m, 2H; 2OCH₂), 3.79 (t, J = 5.00 Hz, 2H;

2OCH₂), 3.70 (m, 8H; 4OCH₂), 1.85 ppm (m, 12H, 6CH₂); ¹³C NMR

(125 MHz, CDCl₃, 208C, TMS): d = 185.2, 166.5, 163.0, 153.2, 149.9,

146,7, 146.5, 140.4, 138.7, 137.9, 135.7, 132.0, 129.6, 125.7, 125.1, 122.9,

120.5–108.2 (several CF multiplets), 108.0, 73.0, 71.2, 71.15, 71.10, 71.0,

ArH), 4.42 (br, 1H, NCH), 1.71 (br, 4H, 2CH₂), 0.69 ppm (t, J

=

6.33 Hz, 6H; 2CH₃); 24: ¹H NMR (500 MHz, CDCl₃, 208C, TMS): d =

8.63–8.69 (m, 8H; ArH), 5.08 (m, 1H, NCH), 2.23–2.28 (m, 2H, CH₂),

1.92–1.98 (m; 2H; CH₂), 0.93 ppm(t, 6H; 3CH₃).

2-(1-Ethylpropyl)-9-[2-(2-hydroxyethoxy)ethyl]anthra[2,1,9-def;6,5,10-

d’e’f’]diisoquinoline-1,3,8,10(2H,9H) tetraone (25): Compound 24 (2.26 g

A

of a 63:37 mixture of 24/21, 3.08 mmol) was suspended in pyridine

(50 mL) and 2-(2-hydroxy-ethoxy)-ethylamine (2.0 mL, 20.07 mmol) was

added. The reaction mixture was heated under reflux for 70 min, then

poured into water (200 mL) to precipitate a maroon gel. This was filtered

and rinsed with water, removing a violet component. The solid was dried,

suspended in 25% MeOH/CH₂Cl₂(160 mL) and silica gel was added,

and the solvent was removed. This was placed over fresh silica gel and a

fraction rich in product (93%) was eluted with CH₂Cl₂. This was used

without further purification. The byproduct 2,9-bis[2-(2-hydroxy-ethox-

y)ethyl]anthra[2,1,9-def;6,5,10-d’e’f’]diisoquinoline-1,3,8,10-

69.6, 69.2, 68.8, 66.1, 64.6, 30.1 (t, J(C,F) = 22 Hz), 17.7, 17.5 ppm; MS

R

(MALDI-TOF): m/z: calcd for C₆₅H₄₆F₅₁N₃O₁₇: 2109.2; found: 2134.2

[M+Na⁺], 2149.3 [M+K⁺].

2-[2-(4,5,7-Trinitro-9-dicyanomethyleneflourene-2-carboxy]ethyl

3,4,5-

tris(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-

yloxy)benzoate [(3,4,5)12F8G1-2EOTNFDCM]: Malononitrile (0.010 g,

0.15 mmol) was added to a solution of A8 (0.20 g, 0.1 mmol) in DMF

(7 mL) and the mixture was stirred at room temperature for 3 h. MeOH

(10 mL) was added and the resulting precipitate was filtered and dried.

Recrystallization from CH₂Cl₂/MeOH 1:1 gave an orange solid (0.17 g,

C

1

83%). Purity (HPLC): 99+ %; H NMR (500 MHz, CDCl₃, 208C, TMS):

d = 9.64 (t, J = 2 Hz, 1H; ArH), 9.22 (d, J = 2 Hz, 1H; ArH), 8.96 (d,

J = 2 Hz, 1H; ArH), 6.97 (s, 2H; ArH), 4.64–4.63 (t, J = 3.9 Hz, 2H;

208C, TMS): d = 11.2, 26.40, 42.70, 49.50, 62.55, 67.90, 69.11, 70.92,

121.77, 121.9, 128.5, 130.52, 131.12, 166.72 ppm.

Chem. Eur. J. 2007, 13, 3330 – 3345

ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

3343

V. Percec et al.

2-(1-Ethylpropyl)-9-[2-(2-hydroxy-ethoxy)ethyl]perylenetetracaboxydi-

imide-4,5-tris(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-do-

decan-1-yloxy)benzoate [(3,4,5)12F8G1-2EOPBI]: Triphenylphosphine

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(40 mg, 0.15 mmol) was added to

a stirred solution of 1 (96 mg,

0.06 mmol) in dry THF (8 mL) under Ar at room temperature. Com-

pound 25 (40 mg, 0.075 mmol, in 2 mL THF) was added to the reaction

mixture, followed by DIAD (30 mL, 0.15 mmol). The reaction mixture

was stirred at room temperature for 24 h. The solvent was evaporated by

rotary evaporation and the crude residue was purified by column chro-

matography (silica gel, EtOAc/hexane 1:1) followed by precipitation in

cold methanol to yield a dark red powder (55 mg, 43%). Purity (HPLC):

99+ %; R_f= 0.37 (silica gel, EtOAc/hexane 1:1); ¹H NMR (500 MHz,

CDCl₃, 208C, TMS): d = 0.93 (t, J = 7.5 Hz 6H; CH₃), 1.80 (m, 12H;

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(CH₂)₂CF₂), 1.95 (m, 2H; CH₂CH₃), 2.11 (m, 6H; CH₂(CH₂)₂CF₂), 2.27

R

(m, 2H; CH₂CH₃), 3.89–3.96 (overlapped t, 10H; CH₂O and

CH₂OArCO), 4.42–4.48 (overlapped m, 4H; CH₂OCO and NCH₂), 5.08

(m, 1H; CHN), 7.16 (s, 2H; ArH ortho to CO₂), 8.56–8.67 ppm (overlap-

ped d, 8H; ArH perylene ring); ¹⁹F NMR (CDCl₃, 470 MHz, 278C): d =

ꢀ81.3 (overlapped t, 9F; CF₃), ꢀ114.9 (m, 6 F; CF₂CH₂), ꢀ122.4 (m,

18F; (CF₂)₃CF₂CH₂), ꢀ123.2 (s, 6F; CF₃(CF₂)₂CF₂), ꢀ124.6 (m, 6F;

N

CF₃CF₂CF₂), ꢀ126.6 ppm (m, 6F; CF₃CF₂); ¹³C NMR (125 MHz, CDCl₃,

208C, TMS): d = 11.5, 17.3, 17.5, 25.2, 28.9, 29.9, 30.8, 39.4, 57.9, 64.4,

68.1, 68.5, 68.8, 72.8, 108.1, 123.2, 123.4, 124.4, 126.7, 131.7, 134.6, 135.1,

152.6, 163.7 ppm; MS (MALDI-TOF): m/z: calcd for C₇₆H₅₃F₅₁N₂O₁₀

:

2123.16; found: 2124.19 [M ⁺].

Acknowledgements

Financial support by the National Science Foundation (NSF DMR-

0548559 and NSF DMR-0102459) is gratefully acknowledged.

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Received: June 24, 2006

Revised: September 7, 2006

Published online: January 16, 2007

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Article Doi

Self-assembly of semifluorinated minidendrons attached to electron-acceptor groups into pyramidal columns

DOI: 10.1002/chem.200600901

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