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Inorganic Chemistry Communications 11 (2008) 175–178 www.elsevier.com/locate/inoche

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 SÁ Á ÁS 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–HÁ Á ÁO 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 tetrathiafulvalene (TTF) field is to prepare new TTF compounds attached with various functional groups [1–4]. In the field of coordination chemistry, bifunctional TTF derivatives are designed and synthesized in order to introduce 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 investigated. 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, comparing with the TTF-pyridyl metal complexes, very few compounds have been prepared with TTF-carboxylate

ligands. A hexaaquometal TTF salt, two dinuclear Re complexes 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] Á 2DMF Á H2O and [Ni(H2O)6] [Ni(L)2(DMF)2] Á 2DMF Á H2O (L = 8,9-dimethylthio-2,3-dicarboxylate-tetrathiafulvalene).
MeS MeS S S S S COO COO

Corresponding authors. Tel./fax: +86 512 65224783. E-mail addresses: zhuqinyu@suda.edu.cn (Q.-Y. Zhu), daijie@suda. edu.cn (J. Dai). 1387-7003/$ - see front matter Ó 2007 Published by Elsevier B.V. doi:10.1016/j.inoche.2007.12.002

TTF derivative C10H12O7S6Na2 Á 3H2O (Na2L Á 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]2À anions, [Co(H2O)6]2+ cations and

The carboxylate groups of the TTF derivative take the mono-coordinated model. The TTF unit takes a boat configuration with dihedral angle ca. 1. which is a common character found for neutral TTF compounds. Compound 3 has a similar structure as 2. [Co(H2O)6]2+ cations. showing an elongated octahedral geometry with a D4h coordination sphere. The molecular structure and molecular packing of complex 3 are essentially the same as that of complex 2. y. Co(1)–O(3). O(3)–Ni(1)–O(3). Bond distances: Ni(1)–O(1). Short S Á Á Á S contacts assembled a 2D sheet with rectangular grid net (a). Ày + 1. Gu et al.055(3) A and the Co–O (DMF) distances are 2. Àz. z. 1 with labeling scheme. 2. The Co–O (COO) distances are ˚ ˚ 2.54(15)°. hydrogen atoms. 2. 88. 180. solvent molecules (DMF and H2O). and the hexaaquometal cations residing in the cavities of the network fixed by O–HÁ Á ÁO hydrogen bonds (b). bond angle: O(1)–Ni(1)–O(1).00(18)°.99(13)°. 89. ˚ 2. ˚ 2. The structure of 2 is presented in Fig. respectively [18]. The Co atom lies on a center of inversion and is coordinated by four oxygen atoms from four carboxylate groups in the equatorial plane and two oxygen atoms of the DMF molecules in the apical positions.176 J.059(3) A. Crystal structure of the anion in compound 2. 2.0(2)°.055(3). 25° and 20°. Ni(1)–O(3). (iii) x. crystallizing in the monoclinic system with space group C 2 =m. Ày + 1. Bond distances: Co(1)–O(1). (ii) Àx + 1. 180.106(4) A. Symmetry transformations: (i) Àx + 1. O(3)–Co(1)–O(3). Sulfur atoms of the five-membered ring at methylthio group side interact directly with the same sulfur atoms of the neighbouring molecules with SÁ Á ÁS contact distance of Fig. Àz. Both the coordinated and the free DMF molecules are in disorder. / Inorganic Chemistry Communications 11 (2008) 175–178 Fig. which forms two seven-membered coordination rings.028(2).113(4) A. solvents and the atoms of DMF in disorder have been omitted for clarity. All these characters in structure mean that the molecule is a r donor–acceptor system. . bond angle: O(1)–Co(1)–O(1).

The authors also thank Suzhou University for financial support.498(2) A for 2 and 3. and the Ere (1) shift from 0. and the charge distribution per TTF ligand is not changed. The new E1/2(1) locates at 0. a positive potential shift of the data was observed.554 V. Because of the partial hydrolyzation of 1. a single-compartment cell equipped with a platinum working electrode. The molecules were assembled by these short SÁ Á ÁS contacts forming a 2D sheet with rectangular grid net (Fig.556 V) measured in H2O–CH3CN (1:1 v/v) [18].ccdc. which is more stable in higher polar solvent and hydrogen bonding solvent in redox view. 2a). Cyclic voltammograms of compound 1 with increased concentration of cobalt nitrate (versus SCE). Optical diffuse reflectance spectra of the ligand 1 and the cobalt complex 2 (powdered samples.cam. The co-crystallized DMF and water molecules are also interact to the hexaaquometal cations with hydrogen bonds. The CV curve of the ligand 1 shows two quasi-reversible redox waves at E1/2(1) = 0.or HL + M(II) -e M(II) -e +e HL- HL ML2 +e L- L Scheme 1. which is shorter than ˚ the van der Waals distance of 3. since a L2H+ -H+ -e -e +e b L-H+ -e +e L L2.606 V that should be the redox equilibrium of ML2þ =ML2 . the radius of the M(II) ion are larger than that of the proton. and S is the scattering coefficient [23]. The absorption (a/S) data were calculated from the reflectance. This band then can be assigned to the intramolecular charge-transfer absorption. 3.70 V in the first redox process.280 and 0. / Inorganic Chemistry Communications 11 (2008) 175–178 177 ˚ ˚ 3. Comparing with the data of 1 (0. at room-temperature). the metal ion ionized from the ligand and E1/2 of the second step has not shifted remarkably. Fig. When the compound was further oxidized. since the redox properties of TTF derivatives have been well characterized.uk/data_ Fig. The hexaaquometal cations [Co(H2O)6]2+ reside in the cavities of the 2D network and are fixed by O–HÁ Á ÁO hydrogen bonds with the oxygen atoms of carboxylate group of the TTF derivative (Fig. 4). reference).J. that is the oxidation of the protonated salt. When added Ni(NO3)2 to the redox system.527 to 0. v/v) at room temperature (Fig. 4. a platinum wire counter electrode and a saturated calomel electrode (SCE. The absorption curves of compounds 1 (ligand) and 2 (Co complex) are similar except the band at about 410 nm. It is reasonable that the positive shift of 2 [ML2]2À is smaller than that of the HLÀ species.818 V with DE(Eox À Ere) = 66 and 98 mV.506(2) A for 3. HLÀ to HL [18]. respectively. a new peak ðE0ox ð1ÞÞ appears at 0. the two oxidation peaks in first step disappeared but a new peak at Eox (1) = 0.658 V appeared.560 V and E1/2(2) = 0.60 A. Room-temperature optical diffuse reflectance spectra of the powdered samples were obtained (Fig. Gu et al. The result is reasonable. 3). These data can be The Cambridge Crystallowww. using a three-electrode system. Appendix A. Supplementary material CCDC 656548 and 656549 crystallographic data for this obtained free of charge from graphic Data Centre via contain the supplementary paper. Acknowledgements This work was supported by the National Natural Science Foundation (20071024) and the Education Committee of Jiangsu province (00KJB150001). PR China. . since the redox active species is a dicarboxylate anion. 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. 2b).ac. All these reactions are summarized in Scheme 1. TTF+/TTF and TTF2+/TTF+. which shifts to 460 nm when the complex formed. The results can be assigned as the two-step one-electron oxidations. In the second redox process. where a is the absorption. only one pair of peak appeared.

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