Synthesis and properties of a new coumarin functionalized tetrathiafulvalene derivative

Article abstract of DOI:10.1002/jccs.201200561

Anew tetrathiafulvalene (TTF) derivative possessing Schiff base core with the coumarin moiety has been synthesized and characterized. The crystal structure has been studied, and the electrochemical and spectroscopic properties have also been investigated. Optimized conformation and molecular orbital diagram of the title compound have been calculated with density functional theory (DFT).

Full text of DOI:10.1002/jccs.201200561

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Synthesis and Properties of a New Coumarin Functionalized Tetrathiafulvalene
Derivative
a
a
a
b,
Liang Hu, Rong-Mei Zhu, Jie Qin and Xin-Hui Zhou *
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National
a
Laboratory of Microstructures, Nanjing University, Nanjing 210093, People’s Republic of China
b
Key Laboratory for Organic Electronics & Information Displays (KLOEID) and Institute of Advanced Materials (IAM),
Nanjing University of Posts & Telecommunications (NUPT), Nanjing 210023, China
(Received: Oct. 28, 2012; Accepted: Jan. 28, 2013; Published Online: Mar. 21, 2013; DOI: 10.1002/jccs.201200561)
A new tetrathiafulvalene (TTF) derivative possessing Schiff base core with the coumarin moiety has been
synthesized and characterized. The crystal structure has been studied, and the electrochemical and spec-
troscopic properties have also been investigated. Optimized conformation and molecular orbital diagram
of the title compound have been calculated with density functional theory (DFT).
Keywords: Coumarin; Tetrathiafulvalene.
INTRODUCTION
Tetrathiafulvalene (TTF) and its derivatives have
EXPERIMENTAL
2-(4,5-Bis(methylthio)-1,3-dithiol-2-ylidene)benzo[d][1,3]
dithiol-5-amine (L ) was synthesized according to the literature
been extensively studied for their unique p-electron donor
in the field of conducting organic materials involving inter-
molecular charge-transfer(CT) interactions with various
3
1
8
procedure. Elemental analyses for C, H and N were determined
using a Perkin-Elmer 240C analyzer. Infrared spectra were re-
1
-2
-1
p-accepting molecules (A). Topics of interest for intra-
corded in the 400-4000 cm region by Vector22 Bruker spectro-
molecular D-Amolecules in general also include molecular
photometer with KBr pellets. UV-VIS spectra were obtained on a
UV-3100 spectrophotometer. Emission measurements were car-
ried out on AMINCO Bowman Series 2 luminescence spectrome-
ter in a 1 cm quartz cell. Mass spectra were determined with
3
4
electronic devices, chromophores for dyes and nonlinear
5
optics. In the last two decade, considerable effort has been
devoted to association of the TTF core with various func-
tional groups that are covalently grafted through a p- or
s-bonded molecular bridge for enhancement of the inter-
molecular interactions among electron donors and accep-
1
GC-TOF instrument for EI-MS. H NMR spectra were recorded
on a Bruker AM 500 instrument. Cyclic voltammetry was per-
formed on an Im6eX electrochemical analytical instrument, with
a glassy carbon as the working electrode, a platinum as the coun-
6
tors, A series of substituent heteroatombased ligands such
3
a,7
8
+
as tetracyano-p-quinodimethane, quinones, electron-
ter electrode, Ag/Ag as the reference electrode, and 0.1 M n-
9
10
deficient aryl groups, pyridinium and bipyridinium
Bu
4
NClO
4
as the supporting electrolyte.
11
12
13
units, fullerenes, phthalocyanines, and mesomerically
Procedure for the synthesis of 3-methyl-coumarin (L ).
1
1
4
15
16
conjugated carbonyl, thiocarbonyl, and ester, are
linked to the TTF core to control of the structural, elec-
tronic, optical, and magnetic properties arising from ICT
interactions in the ground state, or in the excited state.
Meanwhile, coumarins are an important class of fluo-
2-Hydroxybenzaldehyde (5.27 g, 43.2 mmol), sodium propionate
(9.0 g, 93.6 mmol) and propionic anhydride (15 mL, 117 mmol)
were placed in a 100 mL round-bottom flask. Triethylamine (6
mL, 43.2 mmol) was then added via the addition funnel, and the
reaction mixture was heated to reflux for 6 h. After the reaction,
water (30 mL) was poured and the resulting pink solid was col-
lected by filtration and washed with cold water. Column chroma-
tography (dichloromethane: petroleum ether = 1:1) of the crude
1
7
rescent and p-accepting compounds, while TTF moiety
can be reversibly oxidized to the corresponding cationic
+
2+
radical (TTF ) and dication (TTF ). In order to investigate
the property changes of TTF caused by coupled moiety of
coumarin and the intermolecular charge-transfer(CT) in-
teractions between TTF and coumarin, a new TTF deriva-
tive possessing Schiff base core with the coumarin moiety
has been synthesized and characterized for the first time.
1
product over silica gel gave L as a colorless powder. Yield: 3.63
1
g (52.5%). H NMR (500 MHz, DMSO): 2.08 (s, 3H), 7.31 (t, J =
8.0 Hz, 1H), 7.34 (d, J = 8.5 Hz, 1H), 7.52 (t, J = 8.0 Hz, 1H), 7.60
(dd, J12 = 1.0 Hz and J13 = 7.5 Hz, 1H), 7.84 (s, 1H), EI-MS, m/z
+
(relative intensity): 160.0 ([M] , 100).
*
Corresponding author. Fax: +86-25-85866396; Email: iamxhzhou@njupt.edu.cn
J. Chin. Chem. Soc. 2013, 60, 573-578
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573

Article
Hu et al.
Procedure for the synthesis of 3-formyl-coumarin (L
2
).
Table 1. Crystallographic data for compound 1
Formula C H NO S
To a solution of compound L (1.37 g, 8.6 mmol) in 75 mL of CCl
1
4
Z
4
2
2
17
3 6
was added NBS (3.83 g, 21.5 mmol) and a trace amount of AIBN,
and the mixture was then refluxed. After reaction for 8 h, the sol-
vent was removed under reduced pressure. To the resulting resi-
due were added NaOAc (4.23 g, 51.6 mmol) and acetic acid (80
mL), and the mixture was then heated to reflux for 12 h. Subse-
quently, 2 N HCl (20 mL) was added to the hot reaction mixture,
and the reaction was allowed to continue for 30 min. The reaction
mixture was then evaporated to dryness, and the residue was di-
-3
Fw
535.73
Dcalcd, g cm
1.475
296
crystal
system
space
group
a , Å
b, Å
c, Å
a, deg
b, deg
g, deg
monoclinic
T / K
-1
P2 /c
m, mm
0.592
1104
1
15.361(2)
4.9028(6)
32.090(5)
90
93.544(3)
90
F(000)
Reflections collected 16694
Unique reflections
4720
1.046
0.0362
2
GOF (F )
R
int
a
b
rectly purified by chromatography on silica gel (CH
2
Cl
2
: petro-
R , wR (I > 2s(I)) 0.0664, 0.1893
1
2
3
a
b
leum ether = 1:1) to afford L
2
as a yellow powder. Yield: 1.25 g
V, Å
2412.1(6)
R
1
, wR
2
(all data)
0.0861, 0.2126
1
a
b
2
2 2
2 2 1/2
(
(
83.6%). H NMR (500 MHz, DMSO): 7.44 (t, J = 8 Hz, 1H), 7.48
R = S||C| - |F ||/S|F |. wR = [Sw(F - F ) /Sw(F ) ]
1 c o 2 o c o
d, J = 8.5 Hz, 1H), 7.78 (t, J = 7.5 Hz, 1H), 7.97 (dd, J12 = 1.0 Hz
and J13 = 7.5 Hz, 1H), 8.67 (s, 1H), 10.02 (s, 1H) ppm. EI-MS, m/z
Table 2. Selected bond distances (Å) and angles (°) for
compound 1
+
(
relative intensity): 174.0 ([M] , 100).
Procedure for the synthesis of L
a
-Imine-4-coumarin (1).
(0.18 g, 0.50 mmol), L
C1-O1
C9-O1
C8-C10
C11-N1
C17-S1
C18-S4
O1-C1-C6
N1-C10-C8
C13-C11-N1
C10-N1-C11
S2-C17-S1
S4-C18-S3
C19-S5-C21
1.368(6)
1.377(6)
1.452(6)
1.417(5)
1.755(4)
1.748(5)
121.1(4)
121.5(5)
125.2(4)
121.4(4)
115.5(2)
114.5(2)
103.2(3)
C8-C9
C9-O2
C10-N1
C16-S1
C17-C18
C20-S4
O1-C9-C8
C12-C11-N1
C12-C11-C13
C16-S1-C17
C18-C17-S1
C19-S3-C18
C22-S6-C20
1.446(7)
1.201(7)
1.260(6)
1.746(4)
1.339(6)
1.759(5)
117.7(5)
115.2(4)
119.6(4)
95.2(2)
This ligand was obtained by mixing L
3
2
(
0.087 g, 0.50 mmol) and a catalytic amount of formic acid in 12
mL of distilled ethanol at refluxing temperature. After stirring for
h, red precipitates were filtered off, washed with ethanol and
6
dried under vacuum. Red crystals suitable for X-ray diffraction
were obtained from evaporation of the solution of dichloro-
-
1
methane and acetonitrile mixture. Yield: 83%. IR (KBr, cm ):
3
422, 2918, 2360, 1716, 1626, 1607, 1558, 1454, 1287, 1177,
122.5(3)
95.6(2)
94.0(4)
1
1
120, 1052, 976, 857, 750, 731. H NMR (500 MHz, DMSO, d):
8
.77 (s, 1H), 8.64 (s, 1H), 7.96 (d, J = 7.5 Hz, 1H), 7.72 (t, J = 8.5
Hz, 1H), 7.57 (d, J = 8.5 Hz, 2H), 7.48 (d, J = 8.5 Hz, 1H), 7.43 (t,
J = 8.5 Hz, 1H), 7.20 (dd, J12 = 2.0 Hz and J13 = 8.5 Hz, 1H), 2.45
+
(
s, 6H). EI-MS, m/z (relative intensity): 517.0 ([M] , 100).
Structure determination. The X-ray diffraction data were
RESULTS AND DISCUSSION
As indicated in Scheme I, 3-methyl-coumarin (L
and 3-formyl-coumarin (L ) were prepared similar to the
literature methods, respectively. Compound 1 was pre-
pared by the reaction of 3-formyl-coumarin (L ) with L .
1
)
collected on a Bruker Smart Apex CCD diffractometer equipped
with graphite monochromated Mo Ka (l = 0.71073 Å) radiation
using a w-2q scan mode at 296 K. The highly redundant data sets
were reduced using SAINT and corrected for Lorentz and polar-
ization effects. Absorption corrections were applied using
2
2
1
2
3
All compounds are soluble in most organic solvents and air
stable in both solution and solid state. Characterization of
1
9
1
SADABS supplied by Bruker. The structure was solved by direct
all compounds has been accomplished by IR, H NMR,
2
methods and refined by full-matrix least-squares methods on F
UV-vis and mass spectra.
2
0
using SHELXTL-97. All non-hydrogen atoms were found in al-
ternating difference Fourier syntheses and least-squares refine-
ment cycles and, during the final cycles, refined anisotropically.
Hydrogen atoms were placed in calculated positions and refined
as riding atoms with a uniform value of Uiso. Crystallographic de-
tails and selected bond lengths and angles for 1 have been summa-
rized in Tables 1 and 2. The Crystallographic data of 1 have been
deposited in CCDC with the reference number of 886593.
The electrochemical properties of compound 1 were
investigated using cyclic voltammetry in CH Cl /CH CN
2
2
3
-
1
(1:1 ratio, 0.1 mol·L n-Bu NClO ). As shown in Figure 1,
4
4
compound 1 exhibits two reversible single-electron redox
couples at 0.456 and 0.736 V, corresponding to the succes-
0
sively reversible oxidation of neutral TTF (TTF ) to the
+
2+
radical cation (TTF ) and then to the dication (TTF ). As
can be seen by comparing the oxidation of compound 1
574
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JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
A Coumarin Functionalized Tetrathiafulvalene Derivative
Scheme I Synthetic route to compound 1
on the TTF moiety, whereas the LUMO is mostly located
on electron acceptor fragment-coumarin moiety. As a re-
sult, the calculation determined value from the energy gap
between the HOMO and the LUMO is 2.65 eV (459 nm),
while the experimental determined value is 464 nm. Good
agreement between calculation and experiments further il-
lustrates the contributions of TTF and the accepting group
involved in the charge transfer characters. Thus, the broad
band in the region 426-600 nm can be assigned as intra-
molecular charge transfer (ICT) from the HOMO in TTF to
the LUMO in the electron-accepting coumarin unit.
2 2
The absorption spectra of compound 1 in CH Cl so-
1
2
with that of L (E ox = 0.321 V, E ox = 0.608 V), the two
3
lution at different amount of HCl are shown in Figure 4.
Addition of a stoichiometric mole ratio of HCl causes a dra-
matic change in color from orange to colorless, which is ac-
waves are positively shifted by about 135 and 128 mV, re-
spectively. These shifts indicate a relatively high degree of
CT between the TTF and the coumarin fragment, thus caus-
ing the TTF moiety to be partially charged, and therefore,
more difficult to oxidize.
The electronic absorption spectra of compounds L ,
2
–
5
L and 1 in dichloromethane (c = 5.0 ´ 10 M) are shown
3
in Figure 2. The UV/Vis spectrum of compound 1 shows
strong absorption bands at high energy (l < 350 nm) that
2
2
can be assigned to the intraligand p–p* transition, and a
moderate absorption band (426-600 nm) at lower energy
can be assigned to intramolecular charge transfer (ICT).
The calculations at the density functional theory B3LYP/
*
23
24
6
-31G level, available in GAUSSIAN 03, were carried
out to understand the electronic transition in compound 1
Figure S1). The frontier orbital resulting from the calcula-
tions is presented in Figure 3. In analogy to other TTF(do-
Fig. 2. UV/Vis absorption spectra of compounds L ,
2
–
5
(
3 2 2
L , and 1 in CH Cl solution (c = 5.0 ´ 10 M).
2
5
nor)-acceptor compounds, the HOMO is mainly located
Fig. 1. Cyclic voltammogram for compound L
3
and 1
CN solution (1/1,
(0.1 M) at a sweep rate
-
4
(
5 ´ 10 M) in CH
2
Cl
2 3
/CH
v/v) with n-Bu
4
NClO
4
Fig. 3. Molecular orbital diagram of the HOMO and
of 100 mV/s.
LUMO of compound 1.
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575

Article
Hu et al.
companied by the formation of a new peak centered at
about 307 nm as well as decrease of band from 324 to 600
nm. And the chemical oxidative titrations of compound 1
mum at 420 nm. The significant enhancement in fluores-
cence intensity is observed with the increasing amount of
HCl (Figure 6). It was envisioned that compound 1 is “off”
in fluorescence due to a photoinduced charge-transfer
(PCT) process (from the electron-donating TTF moiety to
the coumarin ring), which quenches the excited state emis-
by using NOPF
sorption spectrophotometry. As shown in Figure 5, When
an acetonitrile solution of NOPF was introduced, the elec-
6 2 2
were made in CH Cl monitored by ab-
6
2
8
tronic spectra of compound 1 showed an increased inten-
sity of the band at 445 nm and the appearance of a new band
at 939 nm, which can be ascribed to the formation of TTF
sion of the coumarin fluorophore. However, upon addi-
tion of HCl, compound 1 is hydrolyzed to release highly
2
fluorescent coumarin dye L .
+
26
radical cation (TTF ), when the oxidation process contin-
ued further, both the new band at 939 nm and the increased
band at 445 nm disappeared, a new band at 742 nm formed,
The orange crystal of 1 suitable for X-ray structural
analysis was obtained by slow evaporation of a mixture so-
lution of CH
and values of R
tion parameters, selected bond lengths and angles are listed
in Table 2. Compound 1 crystallizes as a 1:1 H O solvate.
2
Cl
2
and CH
3
CN. Final crystallographic data
2
+ 27
which belongs to the formation of TTF dication (TTF ),
and a spectacular color change in the solution of compound
1
and wR
2
are listed in Table 1. Data collec-
1
from orange to light green was observed.
2
Furthermore, on excitation at 362 nm, compound 1
The TTF backbone is nearly planar with a dihedral angle of
4.88° between the two five-membered rings (containing
S1, S2, S3, and S4), and the average deviation from a
least-squares plane is only 0.0378 Å. The TTF moiety and
Schiff base group are nearly planar, forming a dihedral an-
gle of 13.9°. And the dihedral angle between TTF moiety
and the coumarin moiety is 11.0°. Due to crystal packing
effects, the methyl substituents in compound 1 are arranged
in a distinctly out-of-plane conformation, and the two
methyl groups are on the same side (Figure 7).
shows very weak fluorescence with a wavelength maxi-
CONCLUSIONS
In summary, a new coumarin-functionalized TTF
compound 1 with p-conjugated Schiff base ligand has been
synthesized. The electrochemical and spectroscopic behav-
ior of compound 1 has been studied. Meanwhile, the chem-
Fig. 4. UV/Vis absorption spectra of compound 1 in
2 2
CH Cl solution upon titration with HCl. Ar-
rows show the evolution of the bands when HCl
is added.
6
ical oxidative titration of compound 1 by NOPF leads to
Fig. 6. Fluorescence spectra of compound 1 in CH
2
Cl
5 ´ 10 M) in the presence of different
amounts of HCl.
2
-
5
(
Fig. 5. UV/Vis absorption spectra of compound 1 in
2 2 6
CH Cl solution upon titration with NOPF .
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JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
A Coumarin Functionalized Tetrathiafulvalene Derivative
Pilkington, M.; Decurtins, S. J. Org. Chem. 2002, 67, 3160;
(
f) Xu, W.; Zhang, D. Q.; Li, H. X.; Zhu, D. B. J. Mater.
Chem. 1999, 9, 1245.
7
. (a) De Miguel, P.; Bryce, M. R.; Goldenberg, L. M.; Beeby,
A.; Khodorkovsky, V.; Shapiro, L.; Niemz, A.; Cuello, A. O.;
Rotello, V. J. Mater. Chem. 1998, 8, 71; (b) Panetta, C. A.;
Baghdadchi, J.; Metzger, R. M. Mol. Cryst. Liq. Cryst. 1984,
1
07, 103.
8
9
. (a) Moriarty, R. M.; Tao, A.; Gilardi, R.; Song, Z.; Tuladhar,
S. M. Chem. Commun. 1998, 157; (b) Watson, W. H.; Eduok,
E. E.; Kashyap, R. P.; Krawiec, M. Tetrahedron 1993, 49,
3035; (c) Frenzel, S.; Müllen, K. Synth. Met. 1996, 80, 175.
. (a) Le Paillard, M. P.; Robert, A.; Garrigou-Lagrange, C.;
Delhas, P.; Le Magueres, P.; Ouahab, L.; Toupet, L. Synth.
Met. 1993, 58, 223; (b) Robert, A.; Lorcy, D. In Molecular
Engineering for Advanced Materials; Becher, J.; Schaumburg,
K., Eds.; Kluwer: Dordrecht, The Netherlands, 1995; p 251.
Fig. 7. Molecular structure of compound 1 with ther-
mal ellipsoids at 30% probability level.
+
the formation of TTF radical cation (TTF ) and TTF dica-
2
+
tion (TTF ) bands, respectively. However, addition of
HCl, compound 1 is hydrolyzed to release highly fluores-
1
0. (a) Goldenberg, L. M.; Becker, J. Y.; Paz-Tal Levi, O.;
Khodorkovsky, V. Y.; Bryce, M. R.; Petty, M. C. J. Chem.
Soc., Chem. Commun. 1995, 475; (b) Goldenberg, L. M.;
Becker, J. Y.; Paz-Tal Levi, O.; Khodorkovsky, V. Y.;
Shapiro, L. M.; Bryce, M. R.; Cresswell, J. P.; Petty, M. C. J.
Mater. Chem. 1997, 7, 901.
2
cent coumarin dye L .
ACKNOWLEDGEMENTS
This work was supported by the Major State Basic
Research Development Program (2011CB808704), the Na-
tional Natural Science Foundation of China (21021062,
11. (a) Simonsen, K. B.; Zong, K.; Rogers, R. D.; Cava, M. P.;
5
1173075 and 21001065) and the Natural Science Founda-
tion of the Jiangsu Higher Education Institutions of China
12KJB150017).
Becher, J. J. Org. Chem. 1997, 62, 679; (b) Simonsen, K. B.;
Thorup, N.; Cava, M. P.; Becher, J. Chem.Commun. 1998,
9
01.
(
1
2. (a) Prato, M.; Maggini, M.; Giacometti, C.; Scorrano, G.;
Sandona, G.; Farnia, G. Tetrahedron 1996, 52, 5221; (b)
Martín, N.; Sµnchez, L.; Seoane, C.; Andreu, R.; Garín, J.;
Orduna, J. Tetrahedron Lett. 1996, 37, 5979; (c) Martín, N.;
Sµnchez, L.; Seoane, C.; Andreu, R.; Garín, J.; Orduna, J.;
Ortí, E.; Viruela, P. M.; Viruela, R. J. Phys. Chem. Solids
REFERENCES
1
. (a) Bendikov, M.; Wudl, F.; Perepichka, D. F. Chem. Rev,
004, 104, 4891; (b) Segura, J. L.; MartOn, N. Angew.
2
Chem., Int. Ed. 2001, 113, 1416; (c) Coronado, E.; Day, P.
Chem. Rev. 2004, 104, 5419.
1
997, 58, 1713.
2
3
. Canevet, D.; Salle, M.; Zhang, G.-X.; Zhang, D.-Q.; Zhu,
D.-B. Chem. Commun. 2009, 2245 and further references
therein.
1
3. Wang, C.; Bryce, M. R.; Batsanov, A. S.; Stanley, C. F.;
Beeby, A.; Howard, J. A. K. J. Chem. Soc., Perkin Trans.
1
997, 2, 1671.
. (a) Aviram, A.; Ratner, M. Chem. Phys. Lett. 1974, 29, 277;
1
1
4. Green, D. C. J. Chem. Soc., Chem. Commun. 1977, 161.
5. (a) Dhindsa, A. S.; Badyal, J. P.; Bryce, M. R.; Petty, M. C.;
Moore, A. J.; Lvov, Y. M. J. Chem. Soc., Chem. Commun.
(
b) Metzger, R. M.; Panetta, C. A. In Molecular Electronic
Devices; Carter, F. L., Ed.; Marcel Dekker: New York, 1987;
Vol. II, p 5.
1
990, 970; (b) Dhindsa, A. S.; Song, Y. P.; Badyal, J. P.;
4
5
. Gordon, P. F.; Gregory, P. Organic Chemistry in Colour;
Springer: Berlin, 1983.
Bryce, M. R.; Lvov, Y. M.; Petty, M. C.; Yarwood, J. Chem.
Mater. 1992, 4, 724.
. (a) Marder, S. R.; Kippelen, B.; Jen, A. K.-Y.; Peyghambarian,
N. Nature. 1997, 388, 845; (b) Verbiest, T.; Houbrechts, S.;
Kauranen, M.; Clays, K.; Persoons, A. J. Mater. Chem. 1997,
1
1
6. Batsanov, A. S.; Bryce, M. R.; Heaton, J. N.; Moore, A. J.;
Skabara, P. J.; Howard, J. A. K.; Ortí, E.; Viruela, P. M.;
Viruela, R. J. Mater. Chem. 1995, 5, 1689.
7
, 2175.
7. (a) Wang, J.; Qian, X.; Cui, J. J. Org. Chem. 2006, 71, 4308;
6
. (a) Andreu, R.; Malfant, I.; Lacroix, P.; Cassoux, P. Eur. J.
Org. Chem. 2000, 3, 737; (b) Xue, H.; Tang, X.-J.; Wu, L.-Z.;
Zhang, L.-P; Tung, C.-H. J. Org. Chem. 2005, 70, 9727; (c)
Zhao, Y.-P.; Wu, L.-Z.; Si, G.; Liu, Y.; Xue, H.; Zhang, L.-P.;
Tung, C.-H. J. Org. Chem. 2007, 72, 3632; (d) Cosquer, G.;
Pointillart, F.; Le Gal, Y.; Golhen, S.; Cador, O.; Ouahab, L.
Dalton Trans. 2009, 3495; (e) Liu, S.-X.; Dolder, S.;
(
b) Woodroofe, C. C.; Lippard, S. J. J. Am. Chem. Soc. 2003,
125, 11458; (c) Yamaguchi, S.; Yoshimura, I.; Kohira, T.;
Tamaru, S.; Hamach, I. J. Am. Chem. Soc. 2005, 127, 11835;
(d) Chen, C. T.; Huang, W. P. J. Am. Chem. Soc. 2002, 124,
6246; (e) Feuster, E. K.; Glass, T. E. J. Am. Chem. Soc. 2003,
125, 16174.
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1
1
8. Qin, J.; Qian, C.-X.; Zhou, N.; Zhu, R.-M.; Li, Y.-Z.; Zuo,
J.-L.; You, X.-Z. Eur. J. Inorg. Chem. 2012, 234.
9. Sheldrick, G. M. SADABSs An Empirical Absorption Correc-
tion Program; Bruker Analytical X-ray Systems: Madison,
WI, 1996.
Chem. 2008, 269; (b) Sun, W.; Xu, C.-H.; Zhu, Z.; Fang,
C.-J.; Yan, C.-H. J. Phys. Chem. C 2008, 112, 16973; (c)
Keniley, L. K.; Ray, Jr., L.; Kovnir, K.; Dellinger, L. A.;
Hoyt, J. M.; Shatruk, M. Inorg. Chem. 2010, 49, 1307; (d) Li,
G.-N.; Xiong, J.; Liao,Y.; Sun, L.; Li, Y.-Z.; Zuo, J.-L. Poly-
hedron 2011, 30. 2473.
2
2
2
0. Sheldrick, G. M. SHELXTL-97; Universität of Göttingen:
Göttingen, Germany, 1997.
26. (a) Andreu, R.; Malfant, I.; Lacroix, P. G.; Cassoux, P. Eur. J.
Org. Chem. 2000, 737; (b) Zhu, Q.-Y.; Liu, Y.; Lu, W.;
Zhang, Y.; Bian, G.-Q.; Niu, G.-Y.; Dai, J. Inorg. Chem.
2007, 46, 10065.
1. Lin, W.-Y.; Yuan, L.; Feng, J.-B.; Cao, X.-W. Eur. J. Org.
Chem. 2008, 2689.
2. (a) Chahma, M.; Wang, X.-S.; van der Est, A.; Pilkington, M.
J. Org. Chem. 2006, 71, 2750; (b) Qin, J.; Hu, L.; Li, G.-N.;
Wang, X.-S.; Xu, Y.; Zuo, J.-L.; You, X.-Z. Organometallics
27. (a) Zhou, Y.; Zhang, D.; Zhu, L.; Shuai, Z.; Zhu, D. J. Org.
Chem. 2006, 71, 2123; (b) Gomar-Nadal, E.; Veciana, L.;
Rovira, C.; Amabilino, D. B. Adv. Mater. 1999, 17, 2095;
(c)Spang-gaard, H.; Prehn, J.; Nielsen, M. B.; Levillain, E.;
Allain, M.; Becher, J. J. Am. Chem. Soc. 2000, 122, 9486.
28. (a) de Silva, A. P.; Gunaratne, H. Q. N.; Gunnlaugsson, T.;
Huxley, A. J. M.; McCoy, C. P.; Rademacher, J. T.; Rice, T.
E. Chem. Rev. 1997, 97, 1515; (b) Valeur, B.; Leray, I. Coord.
Chem. Rev. 2000, 205, 3.
2
011, 30, 2173.
2
2
3. (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098; (b) Lee, C.;
Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
4. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R. et al. Gaussian 03, Revision
B. 05; Gaussian, Inc.: Pittsburgh, PA, 2003.
2
5. (a) Balandier, J.-Y.; Belyasmine, A.; Sallé, M. Eur. J. Org.
578
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