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Inorganic Chemistry Communications 11 (2008) 175–178

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Metal Co(II) and Ni(II) coordination compounds with

tetrathiafulvalene carboxylate
Jing Gu, Qin-Yu Zhu *, Yong Zhang, Wen Lu, Gai-Yan Niu, Jie Dai *
Department of Chemistry, Suzhou University, Suzhou 215123, PR China

Received 21 September 2007; accepted 1 December 2007

Available online 14 December 2007

Abstract

Comparing with the TTF-pyridyl metal complexes, very few compounds have been prepared with TTF-carboxylate ligands. We using
8,9-dimethylthio-2,3-dicarboxylate-tetrathiafulvalene sodium salt as starting material prepared two Co(II) and Ni(II) metal complexes,
[Co(H2O)6][Co(L)2(DMF)2] and [Ni(H2O)6][Ni(L)2(DMF)2]. X-ray structure analysis has revealed that the metal ion is coordinated by
four carboxylate groups from two ligands in the equatorial plane and two DMF molecules in the apical positions. The molecules are
assembled by short S  S contacts forming a 2D sheet with rectangular grid net. The hexaaquometal cations [Co(H2O)6]2+ reside in
the cavities of the 2D network and are fixed by O–H  O hydrogen bonds. Cyclic voltammogram and spectra of the ligand are affected
when the metal ion coordinated.
Ó 2007 Published by Elsevier B.V.

Keywords: Tetrathiafulvalene; Carboxylate; Coordination compound; Crystal structure

In the past decade, one of the most challenges in tetra-
thiafulvalene (TTF) field is to prepare new TTF com-
pounds attached with various functional groups [1–4]. In
the field of coordination chemistry, bifunctional TTF
derivatives are designed and synthesized in order to intro-
duce a coordination moiety that can act as a director of
molecular packing, a magnetic d electron center, and so
on. Among these bifunctional TTF derivatives, a good
established series is pyridine-based TTF derivatives
(TTF-py) [5–12]. Some neutral or radical compounds with
metal coordination bonds have been prepared and investi-
gated. Besides the pyridine ligands, people also have great
interest in carboxylate ligands, for examples, numerous
coordination compounds or polymers have been reported
using the strategy of carboxylate assembly. However, com-
paring with the TTF-pyridyl metal complexes, very few
compounds have been prepared with TTF-carboxylate
Corresponding authors. Tel./fax: +86 512 65224783.
E-mail addresses: zhuqinyu@suda.edu.cn (Q.-Y. Zhu), daijie@suda.
edu.cn (J. Dai).
ligands. A hexaaquometal TTF salt, two dinuclear Re com-
plexes and a Na supramolecular compound have been
characterized crystallographically [13–15]. In this paper,
we report the synthesis, structures and electrochemistry
of two new metal complexes with TTF-carboxylate type
ligand, [Co(H2O)6][Co(L)2(DMF)2]  2DMF  H2O and
[Ni(H2O)6] [Ni(L)2(DMF)2]  2DMF  H2O (L = 8,9-dim-
ethylthio-2,3-dicarboxylate-tetrathiafulvalene).
MeS S S COO
MeS S S COO
TTF derivative C10H12O7S6Na2  3H2O (Na2L  3H2O,
1) was prepared according to the literature [16–18]. Two
Co(II) and Ni(II) metal complexes were crystallized in a
mixed solvent of H2O-DMF under ambient condition for
several days [19,20]. The structures of 2 and 3 were solved
by direct methods using the program SHELX-97 and refined
by SHELXL-97 [21,22]. The structure of compound 2 consists
of [CoL2(DMF)2]2 anions, [Co(H2O)6]2+ cations and

1387-7003/$ - see front matter Ó 2007 Published by Elsevier B.V.

doi:10.1016/j.inoche.2007.12.002
176 J. Gu et al. / Inorganic Chemistry Communications 11 (2008) 175–178
Fig. 1. Crystal structure of the anion in compound 2, hydrogen atoms,
[Co(H2O)6]2+ cations, solvents and the atoms of DMF in disorder have
been omitted for clarity. Symmetry transformations: (i) x + 1, y, z; (ii)
x + 1, y + 1, z; (iii) x, y + 1, z. Bond distances: Co(1)–O(1),
2.055(3); Co(1)–O(3), 2.113(4) Å; bond angle: O(1)–Co(1)–O(1),
88.54(15)°; O(3)–Co(1)–O(3), 180.0(2)°. Compound 3 has a similar
structure as 2. Bond distances: Ni(1)–O(1), 2.028(2); Ni(1)–O(3),
2.059(3) Å; bond angle: O(1)–Ni(1)–O(1), 89.99(13)°; O(3)–Ni(1)–O(3),
180.00(18)°.
solvent molecules (DMF and H2O), crystallizing in the
monoclinic system with space group C 2 =m. The structure
Fig. 2. Short S    S contacts assembled a 2D sheet with rectangular grid net (a), and the hexaaquometal cations residing in the cavities of the network
fixed by O–H  O hydrogen bonds (b).
of 2 is presented in Fig. 1 with labeling scheme. The Co
atom lies on a center of inversion and is coordinated by four
oxygen atoms from four carboxylate groups in the equato-
rial plane and two oxygen atoms of the DMF molecules in
the apical positions. The Co–O (COO) distances are
2.055(3) Å and the Co–O (DMF) distances are 2.106(4) Å,
showing an elongated octahedral geometry with a D4h coor-
dination sphere. The molecular structure and molecular
packing of complex 3 are essentially the same as that of
complex 2. The carboxylate groups of the TTF derivative
take the mono-coordinated model, which forms two
seven-membered coordination rings. The TTF unit takes a
boat configuration with dihedral angle ca. 25° and 20°,
respectively [18], which is a common character found for
neutral TTF compounds. All these characters in structure
mean that the molecule is a r donor–acceptor system. Both
the coordinated and the free DMF molecules are in
disorder.
Sulfur atoms of the five-membered ring at methylthio
group side interact directly with the same sulfur atoms of
the neighbouring molecules with S  S contact distance of
 J. Gu et al. / Inorganic Chemistry Communications 11 (2008) 175–178 177

3.498(2) Å for 2 and 3.506(2) Å for 3, which is shorter than

a b
the van der Waals distance of 3.60 Å. The molecules were
-e -e -
assembled by these short S  S contacts forming a 2D sheet L2- L- L L2- or HL
+e +e +
with rectangular grid net (Fig. 2a). The hexaaquometal cat- M(II)
M(II)
ions [Co(H2O)6]2+ reside in the cavities of the 2D network H+ -H+ -H+
-e -e
and are fixed by O–H  O hydrogen bonds with the oxygen -e ML2 L- L
HL- HL +e +e
atoms of carboxylate group of the TTF derivative
(Fig. 2b). The co-crystallized DMF and water molecules Scheme 1.
are also interact to the hexaaquometal cations with hydro-
gen bonds.
The redox properties of 1 and metal complexes were
studied by cyclic voltammetry (CV) in the mixed solvent
of HPLC grade DMF and ultra purified water H2O (1:1,
v/v) at room temperature (Fig. 3), using a three-electrode
system, a single-compartment cell equipped with a plati-
num working electrode, a platinum wire counter electrode
and a saturated calomel electrode (SCE, reference). The
CV curve of the ligand 1 shows two quasi-reversible redox
waves at E1/2(1) = 0.560 V and E1/2(2) = 0.818 V with
DE(Eox  Ere) = 66 and 98 mV, respectively. The results
can be assigned as the two-step one-electron oxidations,
TTF+/TTF and TTF2+/TTF+, since the redox properties
of TTF derivatives have been well characterized. Compar-
ing with the data of 1 (0.280 and 0.556 V) measured in
Fig. 4. Optical diffuse reflectance spectra of the ligand 1 and the cobalt
H2O–CH3CN (1:1 v/v) [18], a positive potential shift of complex 2 (powdered samples, at room-temperature).
the data was observed. The result is reasonable, since the
redox active species is a dicarboxylate anion, which is more
the radius of the M(II) ion are larger than that of the pro-
stable in higher polar solvent and hydrogen bonding sol-
ton, and the charge distribution per TTF ligand is not
vent in redox view. Because of the partial hydrolyzation
changed. When the compound was further oxidized, the
of 1, a new peak ðE0ox ð1ÞÞ appears at 0.70 V in the first
metal ion ionized from the ligand and E1/2 of the second
redox process, that is the oxidation of the protonated salt,
step has not shifted remarkably. All these reactions are
HL to HL [18]. In the second redox process, only one pair
summarized in Scheme 1.
of peak appeared. When added Ni(NO3)2 to the redox sys-
Room-temperature optical diffuse reflectance spectra of
tem, the two oxidation peaks in first step disappeared but a
the powdered samples were obtained (Fig. 4). The absorp-
new peak at Eox (1) = 0.658 V appeared, and the Ere (1)
tion (a/S) data were calculated from the reflectance, where
shift from 0.527 to 0.554 V. The new E1/2(1) locates at
a is the absorption, and S is the scattering coefficient [23].
0.606 V that should be the redox equilibrium of
The absorption curves of compounds 1 (ligand) and 2
ML2þ2 =ML2 . It is reasonable that the positive shift of
(Co complex) are similar except the band at about
[ML2]2 is smaller than that of the HL species, since
410 nm, which shifts to 460 nm when the complex formed.
This band then can be assigned to the intramolecular
charge-transfer absorption.

Acknowledgements

This work was supported by the National Natural Sci-

ence Foundation (20071024) and the Education Committee
of Jiangsu province (00KJB150001), PR China. The
authors also thank Suzhou University for financial
support.

Appendix A. Supplementary material

CCDC 656548 and 656549 contain the supplementary

crystallographic data for this paper. These data can be
Fig. 3. Cyclic voltammograms of compound 1 with increased concentra- obtained free of charge from The Cambridge Crystallo-
tion of cobalt nitrate (versus SCE). graphic Data Centre via www.ccdc.cam.ac.uk/data_
178 J. Gu et al. / Inorganic Chemistry Communications 11 (2008) 175–178
request/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.inoche.2007.12.002.
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