A novel amphiphilic Re1 complex with bis(fullerene)-substituted bipyridine ligands: Synthesis, electrochemistry, and langmuir film

Article abstract of DOI:10.1002/ejic.200600875

An amphiphilic fullerene (C₆₀) derivative with a (bipyridine)-tricarbonylrhenium(I) chloride polar head group has been prepared. Electrochemical studies indicate that some ground state electronic interactions between the fullerene subunit and the metal complexed moiety are present in Re^I complex 1. The Langmuir film of this compound has been characterized by its surface pressure versus molecular area isotherm and Brewster angle microscopy (BAM) observations. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200600875

SHORT COMMUNICATION
DOI: 10.1002/ejic.200600875
A Novel Amphiphilic ReI Complex with Bis(fullerene)-Substituted Bipyridine
Ligands: Synthesis, Electrochemistry, and Langmuir Film
Hwi Deuk Lee,[a] Sang Keun Oh,[a] Chan Soo Choi,[b] and Kwang-Yol Kay*[a]
Keywords: Rhenium / Fullerenes / Bipyridines / Cyclic voltammetry / Langmuir films
An amphiphilic fullerene (C60) derivative with a (bipyridine)-
tricarbonylrhenium(I) chloride polar head group has been
prepared. Electrochemical studies indicate that some ground
state electronic interactions between the fullerene subunit
and the metal complexed moiety are present in ReI complex
1. The Langmuir film of this compound has been charac-
terized by its surface pressure versus molecular area iso-
therm and Brewster angle microscopy (BAM) observations.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
Introduction
efforts have been made to produce long-lived and high-en-
The fullerene (C60) is an attractive functional group for ergy intramolecular charge separated states, which can be
a large number of multicomponent molecular architectures exploited for practical applications such as solar energy
with photoinduced electron transfer processes[1] because of conversion.[12] Among these, hybrid systems combining the
its electro- and photophysical properties. Fullerene is espe- fullerene with coordination compounds of metal ions such
cially attractive because it can efficiently induce a rapid as RuII,[13] ReI,[13e] and CuI[1g,14] are interesting because the
charge separation accompanied by a slow charge recombi- long-lived metal-to-ligand charge transfer (MLCT) excited
nation.[2] Various donors such as porphyrin,[1f,3] TTFs,[4] state of such complexes has a marked reducing character
ferrocene,[5] pyrene,[6] carbazol,[7] oligothiophenes,[8] N,NЈ- and is capable of initiating photoinduced electron transfer
dialkylaniline,[9] carotenoid,[10] and phthalocyanine[11] have to the fullerene subunit. In fact, the photoelectrochemical
mainly been attached to fullerene (C60) to investigate en- (PEC) devices prepared from fullerene-substituted tris(2,2Ј-
ergy- and electron-transfer interactions. Recently, further bipyridine)ruthenium(II) derivatives have shown the pos-
sibility for a controlled fabrication of the molecular level
devices with high energy conversion efficiencies.[15]
[a] Department of Molecular Science and Technology, Ajou Uni-
versity,
However, only one multicomponent system of such an
Suwon 443-749, South Korea
Fax: +82-31-219-1615
array with a ReI complex[13e] has been reported to date. In
this hybrid system, one fullerene and ReI complex are con-
nected by a long, flexible alkyl linker and have mutual inter-
E-mail: kykay@ajou.ac.kr
[b] Department of Applied Chemistry, Daejeon University,
Daejeon 300-716, South Korea
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H. D. Lee, S. K. Oh, C. S. Choi, K.-Y. Kay
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actions through spatial arrangement of the two compo- LAH produced 3,5-bis(hydroxymethyl)phenol (4) in a yield
nents. Also, no ReI complex with more than one fullerene of 85%. Octadecanol (5) reacted with meldrum’s acid (6) to
substituent has been reported until now, to the best of our afford malonic acid monooctadecyl ester (7) in 89% yield.
knowledge. On the other hand, studies on Langmuir and Esterification of 4 with monoester 7 of malonic acid in the
Langmuir–Blodgett films from amphiphilic fullerene deriv- presence of N,NЈ-dicyclohexylcarbodiimide (DCC) yielded
atives have already been reported by Diederich, Nieren- bis(malonate) 8 (73% yield). The functionalization of C60
garten and others.[16] However, only a limited number of was based on the highly regioselective Diederich reac-
the Langmuir films from fullerene–metal conjugates, such tion,[17] which led to macrocyclic bis adducts of C60 through
as monofullerene–ruthenium(II) coordination compound macrocyclization of the carbon sphere with the bis(malon-
has been reported so far.[13g] In line with these aspects, we ate) derivatives in a double Bingel addition.[18] Treatment
report herein the first synthesis of ReI coordination com- of C60 with 8, iodine, and 1,8-diazabicyclo[5.4.0]undec-7-
pound 1 that possesses a bis(fullerene)-substituted bipyri- ene (DBU) in toluene at room temperature afforded mono
dine ligand, which has short and relatively rigid linkages adduct 9[11b] in 28% yield. The reaction of mono adduct 9
between fullerene and the ReI complex. Furthermore, we with 2,2Ј-bipyridine-4,4Ј-dicarbonyl dichloride (10)[19]
also report its electrochemical properties and Langmuir which was prepared by oxidation of 4,4Ј-dimethyl-2,2Ј-bi-
films.
pyridine with K2Cr2O7 and subsequent conversion of the
diacid to diacyl dichloride 10, went smoothly in the pres-
ence of triethylamine to produce bis adduct 11[20] in 83%
yield. Finally, fullerene-functionalized ligand 11 reacted
with pentacarbonylrhenium(I) chloride in toluene to afford
complex 1[20] in 92% yield.
Results and Discussion
The synthetic route leading to the bis(fullerene)-substi-
tuted 2,2Ј-bipyridine ligand used for the preparation of rhe-
To compare the electrochemical and photochemical
nium(I) complex 1 is depicted in Scheme 1. Commercially properties of ligand 11 and its ReI complex 1, model com-
available 5-hydroxyisophthalic acid (2) was esterified to give pounds 12[20] and 13[20] that lack fullerene moieties were
diester 3 (93% yield), and subsequent reduction of 3 with synthesized in an analogous method (Scheme 2).
Scheme 1. Synthesis of ligand 11 and complex 1: a) MeOH, H2SO4, reflux, 24 h, 93%; b) LiAlH4, THF, reflux, 48 h, 85%; c) Meldrum’s
acid (6), 110–120 °C, 2 h, 89%; d) DCC, DMAP, HOBT, THF, room temp., 12 h, 73%; e) C60, I2, DBU, room temp., 24 h, 28%; f) 10,
Et3N, CHCl3, room temp., 12 h, 83%; g) Re(CO)5Cl, toluene, 80 °C, 12 h, 92%;.
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ReI Complex with Bis(C60)-Substituted Bipyridine Ligands
SHORT COMMUNICATION
Scheme 2. Synthesis of model compounds 12 and 13: a) 8, Et3N, CHCl3, room temp., 12 h, 29%; b) Re(CO)5Cl, EtOH, reflux, 12 h, 86%.
The structure and purity of the new compounds were duction processes. As shown by comparison with corre-
confirmed by 1H NMR and IR spectroscopy, MALDI- sponding ligand 11, which lacks rhenium moiety, complex 1
1
TOF mass spectrometry, and elemental analysis.[20] The H showed five waves (–0.21, –0.69, –1.29, –1.62, and –2.11 V),
NMR spectra of 11 and 1 show the characteristic features which correspond to C60-centered reductions. These re-
of the 1,3-phenylenebis(methylene)-tethered fullerene cis-2 duction waves are regularly spaced around 500 mV. The
bis adduct substituent.[11b,13g] In 11 and 1, a set of AB quar- first three fullerene-centered reduction waves of triad com-
tets are clearly observed for the benzylic CH2 groups (Hf pound 1 are shifted about 30 mV more cathodically with
and Hg) and an AX2 system is revealed for the aromatic respect to those (–0.19, –0.66, and –1.25 V) of the corre-
protons (Hd and He) of the 1,3,5-trisubstituted bridging sponding fullerene model compound, ligand 11. This indi-
phenyl ring. The spectra are also characterized by three sets cates that the LUMO energy levels of the ground state of
of aromatic signals in a typical pattern for a 4,4Ј-disubsti- the fullerene moiety are elevated by ReI complexation.
tuted 2,2Ј-bipyridine (Ha, Hb, and Hc). Thus, the 1H-NMR However, Armaroli et al.[13e] reported that the first two ful-
spectrum of complex 1 is consistent with the proposed lerene-centered reductions of a C60–ReI dyad showed oppo-
structure. Detailed assignments of the peaks in 11 and 1 are site shifts. They suggested that this observation could be a
given and compared with model compounds 12 and 13.[20]
consequence of a small electronic interaction due to spatial
The structure of 1 was also confirmed by mass spectrom- proximity for the two chromophores (more facile fullerene
etry. The MALDI-TOF MS of 1 is characterized by a singly reduction) in C60–ReI. The triad of the present work seems
charged peak at m/z = 3574.81, which can be assigned to 1 to have adopted an extended conformation through rigid
after loss of one chlorine atom.
linkers between fullerene and the ReI complex, which pre-
The electrochemical properties of rhenium(I) complex 1 vents spatial interactions among the chromophores. So, our
and ligand 11 were investigated and compared with those electrochemical results suggest that the electron donation
of model compounds 12 and 13 by cyclic voltammetry (CV) from ReI to fullerene chromophores mainly occurs through
together with differential pulse voltammetry (DPV) in tetra- the bonds. We have to mention that Armaroli et al.[13e] used
hydrofuran (THF) with tetrabutylammonium tetrafluo- a fullerene model compound without a bipyridine ligand,
roborate (TBABF4) as a supporting electrolyte (Table 1). In which does not provide a background for the representation
the negative potential region, complex 1 shows nine re- of only a difference in ReI. Thus, it is difficult to directly
Eur. J. Inorg. Chem. 2007, 503–508
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H. D. Lee, S. K. Oh, C. S. Choi, K.-Y. Kay
SHORT COMMUNICATION
compare their results with the results of the present work. tailed photophysical studies are currently under investiga-
Therefore, the present work only provides more convincing tion and will be reported in due time.
results to explain the electron donating effects of ReI. The
Langmuir films of compound 1 have been characterized
additional waves at –1.00 and –1.48 V that originated from by their surface pressure versus molecular area (π/A) iso-
the bipyridine–malonate domain also shifted negatively therms and Brewster angle microscopy (BAM) observa-
compared with those of ligand 11 (–0.98, –1.43 V). This in- tion.[21] Figure 1 shows a surface pressure/area isotherm (π-
dicates that the complexation of rhenium to the bipyridine A isotherm) of compound 1 on a water surface. Under con-
ligand can influence this negative shift. However, the corre- tinuous compression, the surface pressure started to in-
sponding waves of model compound 13 (–0.97, –1.47 V) crease steeply around 200 Å2/molecule and the Langmuir
showed a relatively large positive shift by the complexation film collapsed around πc ≈ 50 mN/m. The results suggest
of rhenium of corresponding ligand 12 (–1.22, –1.57 V). that compound 1 forms very stable monolayers on the water
The redox processes of ligand 11 were found to have also surface because of the balance between the hydrophobicity
shifted positively from those of ligand 12. These results of the fullerene surrounded by two long alkyl chains and
indicate that the electron-withdrawing C60 group strongly the hydrophilicity of the bipyridine ReI complex. Good re-
affects the characteristics of ligand 11. In model com- versible behavior in the successive compression/expansion
pounds 12 and 13 there are oxidation processes at the redox cycles (data not shown) is also consistent with the amphi-
potentials of 0.81 V (∆Ep = 100 mV) and 0.77 V (∆Ep
=
philic structure of compound 1, where aggregation of fuller-
110 mV), respectively (not shown in Table 1). This may be enes is largely prevented by the long alkyl chains. These
caused by a redox reaction of the aromatic ester group. results are in a good agreement with the previous findings
Interestingly, the negative potential shift of compound 13 on a related amphiphilic fullerene derivative with rutheni-
shows that the oxidation of this group is easier, probably um(II).[13g] The occupied surface area obtained by extrapo-
because of an electron donating function of rhenium. On lation of the steeply rising portion of the π-A isotherm to
the other hand, the additional waves E2 and E8 in Table 1 zero pressure is 166 Å2/molecule, which is very close to the
seem to originate from the metal center because only the molecular area estimated by molecular modeling of com-
compounds with rhenium metal show these waves.
pound 1. A Brewster angle microscope was used to monitor
the structural change of the Langmuir films during com-
pression. The insets of Figure 1 show the BAM images of
the Langmuir films at 200, 300, and 500 Å2/molecule. The
images clearly show that the domain size (brighter regions
in the images) becomes larger as the surface pressure is in-
creased, and a homogeneous monolayer is formed below
200 Å2/molecule.
Table 1. Electrochemical properties of 1, 11, 12, and 13.[a]
Com-
pound E1
Reduction
E4 E5
E2
E3
E6
E7
E8
E9
1
–
–
–
–
–
–
–
–
–
0.21 0.51 0.69 1.00 1.29 1.48 1.62 1.80 2.11
(175) (i) (102) (138) (106) (118) (61) (98) (146)
11
12
13
–
0.19
(93)
–
–
–
–
–
–
0.66 0.98 1.25 1.43 1.75
(96) (96) (111) (98) (125)
2.27
(114)
–
–
1.22
(200)
–
0.97
(110)
1.57
(100)
–
1.47
(100)
–
–
0.49
(100)
1.90
(120)
[a] Cyclic voltammetric measurements: glassy carbon disk working
electrode (3 mm in diameter), Pt wire counter electrode, and silver
wire pseudoreference electrode (Ag/Ag+) were used. The electrolyte
contained degassed THF, 0.1  Bu4NBF4 and 3ϫ10–4  synthe-
sized compounds. The scan rate was 100 mV/s. Values for E1/2 (in
V) as (Epa + Epc)/2 and ∆Ep (in mV) are given in parentheses. DPV
technique was also used to confirm redox potentials, and the results
were in good agreement with CV technique within the first decimal
point. (i) denotes irreversible. The experiments were performed at
ambient temperature and pressure.
Figure 1. π-A isotherm recorded during compression of the mono-
layer of compound 1. The insets are the BAM images of the Lang-
muir films at 200, 300, and 500 Å2/molecule.
Conclusions
The UV/Vis spectrum of 1 in a CHCl3 solution shows
the characteristic absorption features of the fullerene units
We have synthesized a new ReI complex with bis(fuller-
as well as the diagnostic MLCT band of the 2,2Ј-bipyridine ene)-substituted bipyridine ligands, which is a suitable am-
rhenium(I) complex at 380 nm. Interestingly, preliminary phiphilic derivative for the preparation of stable Langmuir
luminescence measurements of 1 in CHCl3 solution (λexc
=
films. Electrochemical properties of this compound have
292 and 380 nm) show strong quenching of the emission by also shown that some ground state electronic interactions
introducing the fullerene moieties in 1, which indicates the between the fullerene subunit and the metal complexed
occurrence of intramolecular photoinduced processes. De- moiety are present in this complex. We are currently investi-
506
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ReI Complex with Bis(C60)-Substituted Bipyridine Ligands
SHORT COMMUNICATION
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Acknowledgments
This work was supported by the Ministry of Education of Korea
(Brain Korea 21 program).
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Selected physical data for 1, 11, 12, and 13. Compound 1: M.p.
1
162 °C. H NMR (200 MHz, CDCl3, 25 °C): δ = 9.38 (d, 1 H,
cArH), 9,02 (s, 1 H, aArH), 8.30 (d, J = 5.1 Hz, 1 H, bArH),
7.68 (s, 1 H, eArH), 7.27 (s, 2 H, dArH), 5.85 (d, J = 12.8 Hz,
2 H, fCH2), 5.25 (d, J = 12.8 Hz, 2 H, gCH2), 4.35 (t, J =
5.2 Hz, 4 H, hOCH2), 1.70 (m, 4 H, jCH2), 1.25 (s, 60 H, iCH2),
0.85 (t, J = 6.4 Hz, 6 H, kCH ) ppm. FTIR (KBr): ν = 2021,
˜
3
1924, 1905, 1750 cm–1. MALDI-TOF MS: m/z = 3574.81 [M –
Cl]+, 721 [C60 + H]+. C235H168ClN2O23Re (3609.58): calcd. C
78.20, H 4.69; found C 78.32, H 4.64. Compound 11: M.p.
1
120 °C. HNMR (200 MHz, CDCl3, 25 °C): δ = 9.25 (s, 1 H,
[9] a) P. V. Kamat, S. Barazzouk, S. Hotchandani, K. G. Thomas,
Chem. Eur. J. 2000, 6, 3914–3921; b) R. M. Williams, J. M.
Zwier, J. W. Verhoeven, J. Am. Chem. Soc. 1995, 117, 4093–
cArH), 9.00 (d, J = 5.1 Hz, 1 H, aArH), 8.10 (d, J = 5.1x Hz,
1 H, bArH), 7.55 (s, 1 H, eArH), 7.27 (s, 2 H, dArH), 5.85 (d,
J = 13.6 Hz, 2 H, fCH2), 5.25 (d, J = 13.6 Hz, 2 H, gCH2),
Eur. J. Inorg. Chem. 2007, 503–508
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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507

H. D. Lee, S. K. Oh, C. S. Choi, K.-Y. Kay
SHORT COMMUNICATION
4.40 (t, J = 6.2 Hz, 4 H, hOCH2), 1.75 (m, 4 H, jCH2), 1.25 (s,
60 H, iCH2), 0.85 (t, J = 6.4 Hz, 6 H, kCH3) ppm. FTIR
4 H, fCH2), 4.12 (t, J = 6.5 Hz, 4 H, gCH2), 3.45 (d, J = 4.7 Hz,
2 H, kCH2), 1.60 (m, 4 H, iCH2), 1.25 (s, 60 H, hCH2), 0.85
(KBr): ν = 1750 cm–1. MALDI-TOF MS: m/z = 3304.21 [M+].
(t, J = 6.4 Hz, 6 H, iCH ) ppm. FTIR (KBr): ν = 2030, 1910,
˜
˜
3
C232H168N2O20 (3303.89): calcd. C 84.34, H 5.13; found C
1900, 1750 cm–1. C115H176ClN2O23Re (2176.32): calcd.
63.47, H 8.15; found C 63.50, H 8.18.
C
84.41, H 4.98. Compound 12: M.p. 84 °C. 1H NMR (200 MHz,
CDCl3, 25 °C): δ = 9.25 (s, 1 H, cArH), 8.96 (d, J = 5.1 Hz, 1 [21] An LB trough (KSV 5000, KSV instruments, Finland) was
H, aArH), 8.05 (d, J = 5.1 Hz, 1 H, bArH), 7.31 (s, 1 H, eArH),
7.27 (s, 2 H, dArH), 5.25 (s, 4 H, fCH2), 4.15 (t, J = 6.5 Hz, 4
H, gCH2), 3.45 (d, J = 4.7 Hz, 2 H, kCH2), 1.60 (m, 4 H,
iCH2), 1.25 (s, 60 H, hCH2), 0.85 (t, J = 6.4 Hz, 6 H, jCH3)
used to form Langmuir monolayers of compound 1 at the
water/air interface. A chloroform solution of compound 1 at a
concentration of 0.05 m was spread onto the water surface of
the LB trough, and then compressed to a surface pressure of
about 60 mN/m. A Brewster angle microscope (BAM, Nanof-
ilm Technology, Germany) equipped with a CCD camera was
used to examine the morphology of the Langmuir films.
Received: September 19, 2006
ppm. FTIR (KBr): ν = 1738 cm–1. C112H176N2O20 (1870.63):
˜
calcd. C 71.91, H 9.48; found C 71.88, H 9.43. Compound 13:
1
M.p.95 °C. H NMR (200 MHz, CDCl3, 25 °C): δ = 9.32 (d, J
= 5.1 Hz, 1 H, cArH), 9.00 (s, 1 H, aArH), 8.27 (d, J = 5.1 Hz,
1 H, bArH), 7.36 (s, 1 H, eArH), 7.27 (s, 2 H, dArH), 5.23 (s,
Published Online: December 19, 2006
508
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 503–508