Phenanthroline- and terpyridine-substituted tetralactam macrocycles: A facile route to rigid di- and trivalent receptors and interlocked molecules

Article abstract of DOI:10.1002/ejoc.201101231

Bromo-substituted Hunter/Voegtle-type tetralactam macrocycles (TLMs) represent key intermediates for the attachment of terpyridyl and phenanthroline metal binding sites through cross-coupling reactions. From these monovalent precursors, metal complexes can easily be obtained that present the macrocycles in a multivalent fashion. Depending on the nature of the metal ion, the properties of the complexes can be tuned with respect to valency (e.g., phen-TLM + Cu^I: divalent, phen-TLM + Fe^II: trivalent) and lability against TLM ligand exchange (e.g., Cu^I: slow, but reversible exchange, Ru^IICl₂: kinetically inert). Hunter/Voegtle-type tetralactam macrocycles are equipped with metal coordination sites through Suzuki cross-coupling. The same bromo-substituted macrocycle can be used irrespective of the individual binding site, which provides versatile access to different complexes. The complexes represent multivalent hosts that are potentially useful for the formation of multiply interlocked molecules. Copyright

Full text of DOI:10.1002/ejoc.201101231

FULL PAPER
DOI: 10.1002/ejoc.201101231
Phenanthroline- and Terpyridine-Substituted Tetralactam Macrocycles: A
Facile Route to Rigid Di- and Trivalent Receptors and Interlocked Molecules
Egor V. Dzyuba,[a] Bilge Baytekin,[a][‡] Dominik Sattler,[a] and Christoph A. Schalley*[a]
Keywords: Supramolecular chemistry / Rotaxanes / Macrocycles / Molecular devices
Bromo-substituted Hunter/Vögtle-type tetralactam macro-
on the nature of the metal ion, the properties of the com-
cycles (TLMs) represent key intermediates for the attach- plexes can be tuned with respect to valency (e.g., phen-TLM
ment of terpyridyl and phenanthroline metal binding sites
through cross-coupling reactions. From these monovalent
precursors, metal complexes can easily be obtained that
present the macrocycles in a multivalent fashion. Depending
+ CuI: divalent, phen-TLM + FeII: trivalent) and lability
against TLM ligand exchange (e.g., CuI: slow, but reversible
exchange, RuIICl2: kinetically inert).
tion chemistry for the construction of multivalent host mo-
lecules from their more easily prepared monovalent ana-
logues reduces the synthetic efforts significantly. Studies of
multivalent binding will certainly benefit from more facile
access to multivalent hosts. Previously, we reported a “tool-
box” of different Vögtle/Hunter-type tetralactam macro-
cycles (TLM) equipped with metal coordination sites. Like
the smaller TLMs of the Leigh type,[16] these tetralactam
macrocycles provide four converging amide groups for in-
teractions with guests Ϫ for example mono- and dicarbonyl
compounds,[17] anions,[14,18] or metal complexes[19] Ϫ and
have thus been used extensively for the construction of me-
Introduction
Multivalent interaction[1] yields significant binding
strength increases in natural noncovalent aggregates, for ex-
ample, when influenza viruses bind to cells. Besides a bind-
ing energy increase, it can also provide control over the
geometry of the interacting particles through multipoint in-
teraction. Viruses, for example, can change the cell surface
to induce endocytosis through multivalent interactions.
For synthetic supramolecular chemistry, multivalency
also promises to be an efficient tool for the construction of
more complex architecture from suitably programmed
building blocks[1c,2] in addition to other concepts in supra-
molecular synthesis such as templation,[3] self-assembly,[4]
and self-sorting.[5] A number of studies on multivalent in-
teractions between synthetic hosts and guests have been
conducted, among them, studies of multivalent calixar-
ene,[6] cucurbit[8]uril,[7] and cyclodextrin complexes[1c,8] and
multiply interlocked (pseudo)rotaxanes,[5c–5e,9] some of
which represent molecular elevators that are switched in re-
sponse to external stimuli.[10] Several multivalent complexes
have been evaluated in detail with respect to the individual
binding contributions[11] and theoretical models exist that
describe them.[12]
chanically
bound
molecules[20]
such
as
rotax-
anes,[15d,18b–18d,18g,18i,21] catenanes,[22] and knots.[23] The
“toolbox” approach, which is extended in the present study,
is expected to be advantageous for the synthesis of multiply
threaded mechanically interlocked molecules.
Results and Discussion
Synthesis of the Phenanthroline- and Terpyridine-
Substituted TLMs 1 and 2
Because highly flexible spacer groups between the bind-
ing sites of a di- or trivalent host may generate entropic
costs upon binding, a rigid connection of the metal binding
site to the TLM would be preferable. Furthermore, at-
taching the coordination site after macrocyclization is ad-
vantageous because this rather low-yielding step is then fin-
ished before the coordination site is attached. Cross-cou-
pling reactions almost perfectly comply with these two
requirements, so we decided to begin the synthesis with the
previously reported bromo-substituted TLM 3.[13] Two syn-
thetic routes have been examined for the synthesis of phen-
anthroline-TLM 1 (Scheme 1). The first attempt to obtain 1
by Miyaura borylation[24] of 3 to yield 7 followed by Suzuki
Based on previous studies[13,14] of metal complexation to
suitably functionalized Hunter/Vögtle-type tetralactam
macrocycles[15] (TLMs), we describe here the synthesis of
different metal complexes of phenanthroline- and terpyrid-
ine-decorated TLMs and rotaxanes. The use of coordina-
[a] Institut für Chemie und Biochemie der Freien Universität
Berlin,
Takustraße 3, 14195 Berlin, Germany
Fax: +49-30-838-55817
E-mail: christoph@schalley-lab.de
[‡] Present address: Non-equilibrium Energy Research Center,
Northwestern University
2145 Sheridan Road, Evanston, IL 60208, USA
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FULL PAPER
Scheme 1. Syntheses of the phenanthroline- and terpyridine-decorated TLMs 1 and 2 from bromo-substituted precursor 3: (a) [Pd-
(PPh3)4], Cs2CO3, toluene/DMF (1:1), 125 °C, 2 d, 92%;[13] (b) NH4OAc, AcOH, 80 °C, 18 h, 74%; (c) [B2(pin)2], KOAc, [Pd(dppf)Cl2],
DMSO, 90 °C, 24 h, 94%; (d) [Pd(PPh3)4], Cs2CO3, toluene/DMF (1:1), 125 °C, 2 d, no product isolated; (e) [Pd(PPh3)4], Cs2CO3, toluene/
DMF (1:1), 125 °C, 2 d, no product isolated; (f) [Pd(PPh3)4], Cs2CO3, toluene/DMF (1:1), 125 °C, 2 d, 66%;[13] (g) 4-bromobenzaldehyde,
NH4Ac, AcOH, 80 °C, 24 h, 86%. [pin = pinacol, dppf = 1,1Ј-bis(diphenylphosphanyl)ferrocene]. The pinacol ester 4 was obtained by
reaction of the corresponding boronic acid with pinacol (1.1 equiv.).[13]
Scheme 2. Synthesis of the di- and trivalent host complexes of 1: (a) [Ru(DMSO)4Cl2], nBuOH, 120 °C, 18 h, 18%; (b) [Cu(MeCN)4-
(PF6)], CH3CN/CH2Cl2 (1:2 v/v), 25 °C, 3 d, quant.; (c) [Fe(BF4)2·6H2O], EtOH, 80 °C, 2 d, quant.
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Substituted Tetralactam Macrocycles
coupling[24b] of 8[25] to this boronic ester-substituted TLM
was, however, unsuccessful. Although the borylation
worked well as described earlier,[13] the subsequent Suzuki
coupling did not yield any detectable product. An alterna-
tive reaction sequence to obtain the TLM 1, i.e., conversion
of bromo-substituted TLM 3 into the aldehyde-substituted
TLM 5 by Suzuki coupling followed by imidazole forma-
tion with diketone 6, worked well and gave the desired
product in 68% overall yield. Similarly, the synthesis of ter-
pyridine-substituted TLM 2 was carried out as reported
previously[13] through Suzuki coupling of boronic ester 10
to bromo-substituted TLM 3. Experiments to optimize this
reaction did not increase the yield to more than 66%.
Moreover, all attempts to use the inverse combination of
boronic ester TLM 7 and the brominated terpyridine pre-
cursor molecule 9 were unsuccessful. Overall, both macro-
cycles can be synthesized with acceptable synthetic efforts
from TLM 3 as the key intermediate.
Metal Complexes of Phenanthroline-Decorated TLM 1
With the phenanthroline-substituted TLM 1, three di-
and trivalent metal complexes were prepared (Scheme 2).
CuI and RuCl2 connect two, and FeII three, TLMs. Because
the single bonds between the phenyl spacer and the TLM
skeleton and imidazole ring are almost freely rotatable, the
connections between the TLM moieties are rigid, but do
not prevent the TLM groups arranging themselves in one
plane with the three cavities in the same directions, thus
providing access for di- and trivalent guests. To obtain the
RuCl2 complex of TLM 1, RuCl3·3H2O was first converted
into [Ru(DMSO)4Cl2].[26] Subsequently, 2 equiv. of TLM 1
were treated with this metal complex precursor in n-butanol
at reflux temperature. The desired RuCl2 complex of 1 was
obtained by column chromatography on neutral alumina.
The rather low yield is likely due to the low solubility of
TLM 1 in almost any organic solvent and water. The cop-
per complex of TLM 1 was prepared by reacting [Cu-
(MeCN)4(PF6)] with 2 equiv. of 1 in CH2Cl2/MeCN. This
Figure 1. Top: Aromatic region of the 1H NMR spectra of (A)
ligand 1 (400 MHz, [D7]DMF) and (B) complex [(1)3Fe(BF4)2]
(500 MHz, [D7]DMF). Peak assignment was secured by 1H,1H
COSY NMR spectroscopy. See Scheme 2 for peak labels. Arrows
indicate typical complexation-induced signal shifts that are simi-
larly observed for the other complexes of 1. Bottom: ESI mass
spectra of (C) [(1)2RuCl2], (D) [(1)2CuPF6] and (E) [(1)3Fe(BF4)2].
Insets: Calculated and experimental isotope patterns.
reaction protocol was adopted from the synthesis of phen- protons, i.e., the protons of the TLM and of the phenyl
anthroline-containing [n]rotaxanes established by Sauvage spacer, do not show significant shift changes. The somewhat
et al.[27] For the synthesis of the trivalent compound, broad NMR signals can be attributed to some aggregation
[(1)3Fe(BF4)2, Fe(BF4)2·6H2O] was used as the iron source. of the TLMs, which is also reflected in their low solubility.
This metal species reacted with 3 equiv. of TLM 1 to afford The other metal complexes exhibit similar complexation-
the desired trivalent complex. The complexes of TLM 1 induced signal shifts, indicating that they also formed.
show a typical dark red-brown color, whereas free 1 is only High-resolution ESI-FTICR mass spectrometry confirmed
slightly yellowish. It should be noted that the ruthenium the clean formation of the desired complexes (Figure 1, C–
and iron complexes are chiral and, of course, form from the E). For the ruthenium complex, peaks at m/z 2649 and 2685
achiral precursors as racemates.
appear that can be assigned to the [(1)2RuCl]+ and
TLM 1 and its metal complexes were fully characterized [(1)2RuCl2 + H]+ ions, respectively. Because it is much less
by NMR and ESI MS analyses. The aromatic regions of energy-demanding to strip off the more weakly binding
the 1H NMR spectra of 1 and [(1)3FeII(BF4)2] are compared BF4– and PF6– counterions during ionization, the other two
in Figure 1 (A and B) as a representative example. Peak complexes are observed as the [(1)2Cu]+ ion (m/z 2572) and
assignments were obtained from H,1H COSY NMR spec- as the doubly charged ion [(1)3Fe]2+ (m/z 1911). Addition-
1
tra. Clearly, the signals for the phenanthroline protons l, m, ally, a small peak at m/z 1256 is visible in the mass spectrum
and n shift significantly to lower field upon complexation of the iron complex; this peak can be assigned to a singly
to the FeII metal core. The signals for all of the more remote protonated TLM 1.
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E. V. Dzyuba, B. Baytekin, D. Sattler, C. A. Schalley
FULL PAPER
FeII Complexes of Terpyridine-Substituted TLM 2 and the
Corresponding Rotaxane 11
To provide clear evidence for the formation of the two
FeII complexes, the corresponding doubly charged parent
ions were mass-selected and fragmented with the aid of a
CO2 laser at a wavelength of 10.6 μm. In this infrared
multiphoton dissociation (IRMPD) experiment, fragmenta-
tion reactions were observed that were perfectly in line with
the structure assignment; the macrocycle complex
[(2)2Fe]2+ dissociated into two singly charged fragments: [(2
+ H)]+ at m/z 1268 and [(2-H)Fe]+ at m/z 1322. Proton
transfer from an amide group of one wheel to the second
macrocycle allows the ion to undergo an energetically favor-
able charge-separating dissociation. Clearly, this fragmenta-
tion reaction confirms the presence of two macrocycles in
2 and their incorporation in the complex. In marked con-
trast, the rotaxane complex [(11)2Fe]2+ fragmented first by
consecutive loss of the two axle groups to yield the interme-
diate [(11)(2)Fe]2+ at m/z 1683 and the macrocycle complex
ion [(2)2Fe]2+. This ion then undergoes the same proton-
transfer-mediated dissociation that was observed for inde-
pendently generated [(2)2Fe]2+ discussed above.
In a similar approach, terpyridine-substituted TLM 2
can be dimerized. Scheme 3 shows the synthesis of rotaxane
11 as described previously,[13,18e] and the preparation of FeII
complexes from both compounds using [Fe(BF4)2·6H2O] as
the metal precursor. These dimers form reversibly at room
temperature quantitatively, and purification is therefore not
1
required. Again, the H NMR spectra show typical com-
plexation-induced signal shifts, although the signals are
broadened significantly because of the low solubility of the
complexes and their strong tendency to aggregate. Al-
though this renders a straightforward NMR analysis diffi-
cult, the complexes can easily be observed by ESI MS as
the doubly charged [(2)2Fe]2+ and [(11)2Fe]2+ ions at m/z
1296 and 2071, respectively, with the expected isotope pat-
terns that confirm the elemental composition (Figure 2). In
addition, the mass spectrum of [(2)2Fe(BF4)2] shows a very
minor (less than 5%) signal at m/z 1930, which corresponds
to a 3:1 complex of 2 and FeII. This signal is due to unspe-
cific aggregation, which often occurs in electrospray ioniza-
tion.[28] The spectrum of the rotaxane complex exhibits a
signal at m/z 1683, which is due to an axle-loss fragment, as
clearly shown by the fragmentation experiments discussed
below.
It should be noted that a one-pot reaction for the forma-
tion of [(11)2Fe(BF4)2] is also possible. When the threading
reaction (Scheme 3, reaction b) was performed either with
[(2)2Fe(BF4)2] as the starting material or simply by mixing
all the reactants required for the rotaxane synthesis in the
Scheme 3. Synthesis of the divalent iron(II) complexes of 2 and of the corresponding rotaxane 11: (a) [Fe(BF4)2·6H2O], CH3CN, 25 °C,
1 h, quant.; (b) dibenzo[18]crown-6, K2CO3, 4-tritylphenol, α,αЈ-dibromo-p-xylene, CH2Cl2, 25 °C, 6 d, 38%.[13]
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Substituted Tetralactam Macrocycles
and more. The combination of different, easy-to-attach co-
ordination sites and a broad choice of metal centers thus
provide a high degree of flexibility. The cross-coupling ap-
proach also ensures that spacers are rigid, thus reducing
the entropic costs of multivalent binding and facilitating the
formation of multiply interlocked rotaxanes.
Experimental Section
General Methods: Reagents were purchased from Aldrich, ACROS,
or Fluka and used without further purification. All reactions were
carried out under a protecting atmosphere of argon. Compounds
3,[13] 5,[13] 7,[13] 8,[25a] 9,[29] 10,[27] and 11[13] were synthesized accord-
ing to literature procedures. The synthesis of 2 and the correspond-
ing analytical characterization has been reported previously;[13] fur-
ther attempts to optimize the yield by using other conditions for
the Suzuki cross-coupling reaction or by using the borylated TLM
7 were not successful. Yields refer to spectroscopically homogen-
eous materials. Solvents were dried and distilled prior to use by
standard laboratory methods. Thin-layer chromatography (TLC)
was performed on precoated neutral alumina plates (Macherey–
Nagel, ALOX N/UV254). Activated neutral alumina (Macherey–
Nagel) was used for column chromatography.
Figure 2. ESI mass spectra of (A) [(2)2Fe(BF4)2] and (C)
[(11)2Fe(BF4)2], which were dissolved in a small amount of DMF
and then diluted with acetone to ca. 100 μm concentration. Spectra
(B) and (D) show infrared multiphoton dissociation (IRMPD) ex-
periments conducted with (B) [(2)2Fe]2+ and (D) [(11)2Fe]2+. In
these experiments, the isolation of the doubly charged precursor
ions was followed by irradiation with a CO2 laser (10.6 μm wave-
length, 100% = 25 W) for 2.5 and 2.0 s, respectively. Insets show
calculated and observed isotope patterns.
1H and 13C NMR spectra were obtained with Bruker ECX 400
(1H: 400 MHz; 13C: 101 MHz) or Jeol ECP 500 (1H: 500 MHz; 13C:
125 MHz) instruments operating at 298 K. All chemical shifts are
reported in ppm with signals of solvent protons taken as internal
standards; coupling constants are given in Hz. The following ab-
breviations are used to indicate NMR multiplicities: s (singlet), d
(doublet), t (triplet), q (quartet), m (multiplet), and br (broad). ESI-
FTICR mass spectra were recorded with an Ionspec QFT-7 instru-
ment (Varian Inc., Lake Forest, CA, USA), equipped with a 7 T
magnet and a micromass Z-spray ESI source (Waters Co., Saint-
Quentin, France). The solvent flow rate was adjusted to 4 μL/min
and the spray voltage was set to 3.8 kV. All other ionization param-
eters were adjusted for optimal signal intensities. UV/Vis spectra
were obtained with a Cary 50 Bio (Varian) instrument by dilution
of a sample of the NMR solution to a concentration of 1.0ϫ10–5
m. Elemental analyses failed because of solvent molecules that were
encapsulated inside the cavities of the macrocycles. These solvents
could not be removed under high vacuum, even upon heating.
Therefore, elemental compositions were assessed by isotope pattern
analysis of the corresponding ions observed in the mass spectra
and/or by exact mass measurements.
presence of half an equivalent of the iron salt, [(11)2Fe-
(BF4)2] also formed. However, this reaction requires that
the product is separated from byproducts such as the
nonthreaded diether axle.
Conclusions
We report a simple, two-step procedure for the introduc-
tion of phenanthroline coordination sites into a Vögtle/
Hunter-type tetralactam macrocycle by using Suzuki cross-
coupling reactions as the key steps. The desired phenan-
throline-decorated TLM is capable of forming metal com-
plexes with metal centers such as RuII, CuI, and FeII that
represent di- and trivalent host molecules that are poten-
tially useful for the investigation of multivalent interlocked
Phenanthroline TLM 1: Aldehyde-decorated TLM
5 (80 mg,
75 μmol), 1,10-phenanthroline-5,6-dione 6 (16.8 mg, 80 μmol) and
NH4Ac (61.6 mg, 800 μmol) were stirred in AcOH (3 mL) at reflux
temperature for 18 h. The resulting solid was filtered hot, washed
with copious amounts of water, and ethanol, and dried under high
molecules. As a complement, the FeII complexes of a terpy- vacuum overnight. TLM 1 (70.3 mg, 74%) was obtained as a
slightly yellow solid; m.p. Ͼ250 °C (dec.). 1H NMR (400 MHz,
ridine-substituted TLM and its corresponding rotaxane
were prepared and characterized. Together with pyridine-
[D7]DMF): δ = 1.43 [s, 9 H, (CH3)3C], 1.55 (br., 4 H, CH2), 1.65
substituted TLMs reported in a previous study,[13] the pres-
(br., 8 H, CH2), 2.21 (s, 12 H, ArCH3), 2.25 (s, 12 H, ArCH3), 2.50
(br., 8 H, CH2), 7.26, 7.27 (2s, 8 H, ArHd,e), 7.89–7.92 (m, 2 H,
ent work demonstrates the versatility of the cross-coupling
approach. Because the metal binding sites can be intro-
duced after the macrocyclization, one key compound, i.e.,
the bromo-substituted TLM, can be used to attach different
coordination sites, which then can be complexed to different
metal centers with a large variety of properties, such as their
3
ArHm), 8.12 (d, J = 7.9 Hz, 2 H, ArHi), 8.23 (s, 2 H, ArHa), 8.53
(s, 2 H, ArHh), 8.60 (d, 3J = 7.9 Hz, 2 H, ArHj), 8.73 (s, 1 H,
3
ArHb), 8.91 (s, 1 H, ArHg), 9.08 (d, J = 7.7 Hz, 2 H, ArHn), 9.13
(d, 3J = 1.9 Hz, 2 H, ArHl), 9.32 (s, 2 H, NHc), 9.48 (s, 2 H, NHf),
14.03 (br., 1 H, NHk) ppm. 13C NMR (125 MHz, [D7]DMF): δ =
15.3, 18.1, 18.5, 18.9, 22.3, 22.6, 26.1, 26.5, 27.1, 28.3, 30.6, 32.2,
oxidation states, coordination geometries, kinetic stabilities 32.8, 36.3, 44.8, 111.1, 114.0, 116.9, 119.7, 125.8, 128.7, 128.7,
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E. V. Dzyuba, B. Baytekin, D. Sattler, C. A. Schalley
FULL PAPER
131.2, 131.3, 132.3, 132.6, 132.7, 132.7, 135.0, 135.8, 145.5, 148.2,
Iron Complex [(2)2Fe(BF4)2]: Terpyridine-substituted TLM 2
150.0, 154.1, 165.1, 167.2 ppm. FTICR-MS (ESI+): calcd. for (30.0 mg, 11.6 μmol) in CD3CN was added to a solution containing
C83H83N8O4 [M + H]+ 1255.6537; found 1255.6561.
the metal precursor [Fe(BF4)2·6H2O] (0.5 equiv.) in CD3CN
+
(0.6 mL). Two drops of CD3OD were added to the mixture (with-
out which the H NMR spectra exhibited only broad signals, indi-
Ruthenium Complex [(1)2RuCl2]: TLM 1 (65 mg, 52 μmol) and
[Ru(DMSO)4Cl2] (12.5 mg, 26 μmol) were stirred in nBuOH
(5.0 mL) and heated to reflux temperature for 18 h. After cooling
to room temperature, the solvent was evaporated under reduced
pressure. The desired divalent ruthenium complex of 1 was ob-
tained after column chromatography over neutral alumina
(CH2Cl2/EtOH, 6:1 v/v) from the first fraction (Rf = 0.8) as a
brown-red solid (25.5 mg, 18%); m.p. Ͼ250 °C (dec.). 1H NMR
(500 MHz, [D7]DMF): δ = 1.44 [s, 18 H, (CH3)3C], 1.56 (br., 8 H,
CH2), 1.66 (br., 16 H, CH2), 2.21 (s, 24 H, ArCH3), 2.28 (s, 24 H,
ArCH3), 2.49 (br., 16 H, CH2), 7.26, 7.29 (2s, 16 H, ArHd,e), 8.18
1
cating aggregation). The resulting mixture was stirred for 30 min
and subjected to analytical characterization without work-up. The
spectra showed a clean product to have formed. The yield of the
desired macrocycle was essentially quantitative. 1H NMR
(500 MHz, CD3CN + 2 drops CD3OD): δ = 1.40 [s, 18 H, (CH3)
3C], 1.53–1.70 (br., 24 H, CH2), 2.17 (s, 24 H, ArCH3), 2.22 (s, 24
H, ArCH3), 2.45 (br., 16 H, CH2), 7.11 (br., 4 H, 2,2ЈЈ-tpy), 7.18
(s, 16 H, ArH), 7.22 (br., 4 H, 3,3ЈЈ-tpy), 7.53 (d, 3J = 6.2 Hz, 4 H,
3
ArH), 7.60 (d, J = 6.2 Hz, 4 H, ArH), 7.63 (s, 4 H, ArH), 7.93 (t,
3J = 6.2 Hz, 4 H, 4,4ЈЈ-tpy), 8.18 (s, 4 H, ArH), 8.24 (s, 2 H, ArH),
8.47 (br., 4 H, 5,5ЈЈ-tpy), 8.50 (s, 2 H, ArH), 8.60 (s, 4 H, 3Ј,5Ј-
tpy), 9.24 (s, 8 H, NH) ppm. FTICR-MS (ESI+): calcd. for
C170H170N14O8Fe2+ [M – 2BF4]2+ 1296.1349; found 1296.1345.
Due to the rather low solubility of the complex, no 13C NMR spec-
trum could be obtained.
3
(d, J = 7.6 Hz, 4 H, ArHi), 8.24 (s, 4 H, ArHa), 8.30–8.39 (m, 4
H, ArHm), 8.56 (s, 4 H, ArHh),8.64 (d, 3J = 7.6 Hz, 4 H, ArHj),
3
8.73 (s, 3 H, ArHb), 8.95 (s, 3 H, ArHg), 9.31 (d, J = 0.9 Hz, 4 H,
3
ArHl), 9.33 (s, 4 H, NHc), 9.40 (d, J = 7.0 Hz, 4 H, ArHn), 9.51
(s, 4 H, NHf), 14.49 (br., 2 H, NHk) ppm. 13C NMR (125 MHz,
[D7]DMF): δ = 15.8, 18.0, 18.3, 19.5, 21.1, 22.6, 27.0, 27.3, 28.1,
31.1, 34.0, 36.2, 44.5, 111.0, 114.3, 116.9, 120.1, 127.0, 128.7, 131.2,
132.3, 132.4, 132.7, 133.2, 135.2, 136.1, 145.6, 148.1, 150.6, 154.2,
165.1, 166.9 ppm. UV/Vis ([D7]DMF, 1.0ϫ10–5 molL–1): λmax (ε
[Lmol–1 cm–1]) = 485 (10.0ϫ103), 370 (7.5ϫ103), 316 (24.6ϫ103),
Iron Complex [(11)2Fe(BF4)2]: Terpyridine-substituted rotaxane 11
(16.0 mg, 7.8 μmol) was treated with [Fe(BF4)2·6H2O] in CD3CN
as described above for [(2)2Fe(BF4)2]; yield quant.; 1H NMR
(500 MHz, CD3CN + 2 drops CD3OD): δ = 1.17 [s, 18 H,
(CH3)3C], 1.32–1.60 (br., 24 H, CH2), 1.73 (s, 24 H, ArCH3), 1.79
(s, 24 H, ArCH3), 2.19 (br., 16 H, CH2), 4.06 (s, 8 H, OCH2), 6.16
241
(48.5ϫ103) nm.
FT-ICR-MS
(ESI+):
calcd.
for
C166H164O8N16ClRu+ 2649.1710; found 2649.1746.
3
3
(s, 8 H, PhHaxle), 6.27 (d, J = 8.7 Hz, 8 H, PhHstopper), 6.87 (d, J
= 8.7 Hz, 8 H, PhHstopper), 6.89 (s, 8 H, ArH), 6.85–6.92 (m, 8 H,
6,6ЈЈ; 3,3ЈЈ-tpy), 6.95–7.17 (m, 60 H, PhHstopper), 7.24 (s, 2 H, ArH),
Copper Complex [(1)2CuPF6]: TLM 1 (20 mg, 16 μmol) was sus-
pended in CH2Cl2 (5 mL) and treated with a solution of [Cu-
(MeCN)4PF6] (3.0 mg, 8 μmol) in CH3CN (2.5 mL). The reaction
mixture was stirred at room temperature for 3 d and then the sol-
vent was exchanged against [D7]DMF for analytical chraracteriz-
ation; yield quant.; m.p. Ͼ250 °C (dec.). 1H NMR (500 MHz, [D7]-
DMF): δ = 1.42 [s, 18 H, (CH3)3C], 1.55 (br., 8 H, CH2), 1.66 (br.,
16 H, CH2), 2.22 (s, 24 H, ArCH3), 2.29 (s, 24 H, ArCH3), 2.49
(br., 16 H, CH2), 7.26, 7.29 (2s, 16 H, ArHd,e), 8.17 (d, 3J = 7.9 Hz,
4 H, ArHi), 8.23 (s, 4 H, ArHa), 8.29–8.34 (m, 4 H, ArHm), 8.54
(s, 4 H, ArHh),8.62 (d, 3J = 7.9 Hz, 4 H, ArHj), 8.71 (s, 3 H, ArHb),
3
7.48 (s, 4 H, ArH), 7.73 (t, J = 7.2 Hz, 4 H, 5,5ЈЈ-tpy), 7.80 (s, 2
3
H, ArH), 7.88 (t, J = 7.2 Hz, 4 H, 4,4ЈЈ-tpy), 7.94 (s, 4 H, ArH),
8.25 (d, 3J = 7.1 Hz, 4 H, ArH), 8.29 (s, 4 H, 3Ј,5Ј-tpy), 8.51 (d, J
3
= 7.1 Hz, 4 H, ArH), 9.09 (s, 8 H, NH) ppm. 13C NMR (125 MHz,
CD3CN + 2 drops CD3OD): δ = 18.5, 22.9, 26.2, 29.5, 30.9, 35.1,
35.3, 45.1, 64.2, 69.6, 117.3, 122.1, 122.6, 125.8, 125.9, 126.5, 127.3,
127.4, 127.5, 127.8, 128.4, 128.7, 130.1, 130.8, 130.9, 131.3, 131.4,
132.2, 134.2, 135.1, 135.2, 135.4, 136.0, 140.1, 141.4, 141.4, 146.8,
148.2, 148.5, 153.6, 156.0, 157.8, 160.2, 166.2 ppm. FTICR-MS
(ESI+): calcd. for C286H262N14O12Fe2+ [M – 2BF4]2+ 2071.4880;
found 2071.4899.
3
8.99 (s, 3 H, ArHg), 9.27 (d, J = 1.0 Hz, 4 H, ArHl), 9.33 (s, 4 H,
NHc), 9.36 (d, 3J = 6.8 Hz, 4 H, ArHn), 9.53 (s, 4 H, NHf),
14.48 (br.,
2
H, NHk) ppm. FTICR-MS (ESI+): calcd. for
C166H164N16O8Cu+ [M – PF6]+ 2572.2214; found 2572.2168. Due
to the rather low solubility of the complex, no 13C NMR spectrum
could be obtained.
Acknowledgments
Iron Complex [(1)3Fe(BF4)2]: TLM 1 (50 mg, 40 μmol) and [Fe(BF4)2·
6H2O] (4.5 mg, 13 μmol) were heated to reflux in EtOH (5 mL) for
2 d. After cooling to room temperature, the solvent was evaporated
under reduced pressure. The residue was dried under high vacuum
and redissolved in [D7]DMF for analytical characterization; yield
This research was funded by the Deutsche Forschungsgemeinschaft
(DFG) (SFB 765, “multivalency”) and the Fonds der Chemischen
Industrie (FCI). E. V. D. thanks the Studienstiftung des Deutschen
Volkes for a PhD scholarship and Dr. Andreas Springer for help
with the ESI-MS experiments.
1
quant.; m.p. Ͼ250 °C (dec.). H NMR (500 MHz, [D7]DMF): δ =
1.44 [s, 27 H, (CH3)3C], 1.55 (br., 12 H, CH2), 1.66 (br., 24 H,
CH2), 2.22 (s, 36 H, ArCH3), 2.26 (s, 36 H, ArCH3), 2.50 (br., 24
3
H, CH2), 7.27, 7.29 (2s, 24 H, ArHd,e), 8.17 (d, J = 7.7 Hz, 6 H,
ArHi), 8.25 (s, 6 H, ArHa), 8.34–8.39 (m, 6 H, ArHm), 8.56 (s, 6
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1176
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Received: August 23, 2011
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