MOLMAT 2010 Conference, July 5-8, 2010, Montpellier, France Zirconium and hafnium coordination compounds with 1,4-dihydroxy-2,5-benzoquinone M. Boltoeva, J. Maynadie, D. Meyer Institut de Chimie Séparative de Marcoule/ Centre de Marcoule, BP 17171, 30207 Bagnols-sur-Céze Cedex, France [email protected] The design and synthesis of multifunctional compounds and materials with predictable structure and properties are one of the topical fields in modern chemistry. The molecular building block approach is now of great interest in the construction of polymeric coordination architectures. These polymers consisting of metal ions and organic ligands as bridges are very promising for processability, flexibility, structural diversity, and geometrical (size, shape, and symmetry) control [1, 2]. Oxocarbon is considered to be one of the most useful multifunctional ligand families. 1,4-dihydroxy-2,5benzoquinone (H2Dhbq) and its derivatives possess coordination, hydrogen bonding and ionic interaction sites, together with redox active π-electronic structures, affording rich coordination chemistry . Although a number of coordination polymers involving Dhbq2- as a bridging ligand have already been reported, our work directed at the synthesis and characterization of new polymeric precursors to ceramic materials is presented. In the present study, we synthesized a series of the zirconium(IV) and hafnium(IV) complexes with Dhbq2- under different experimental conditions. Then, the mixed Zr(IV)/Hf(IV) complexes with various ratios of the metals were prepared. The analytical techniques used were elemental analysis, FTIR and Xray powder diffraction. It was found that the synthesis conditions, namely the nature of the solvent and the temperature are important factors in the complex formation. IR-absorption spectral data indicate the bonding of hydroxyl oxygen and quinone carbonyls with metal ions. The tentative structure of the polymers of Zr(IV) with 1,4-dihydroxy-2,5-benzoquinone is assigned in Scheme 1. O 3+ Zr Cl O O O O Zr Cl O O 3+ Zr O Scheme 1. Structure of coordination polymer of Zr(IV) with 1,4-dihydroxy-2,5-benzoquinone The characterization of obtained complexes by solid-state NMR technique and thermal studies are currently in progress. The preliminary results obtained show that the synthesized compounds are convenient precursors for ceramic materials. The further studies will be performed with metals in various oxidation states (III, IV and V) in order to obtain the mixed valence complexes. References  O.M Yaghi et al., Acc.Chem. Res. 34, 319 (2001).  B.H. Ye et al., Coord. Chem. Rev. 249, 545 (2005).  S. Kitagawa et al., Coord. Chem. Rev. 224, 11 (2002).