Alkali Metal Directed Assembly of Heterometallic V-v/M (M = Na, K, Cs) Coordination Polymers: Structures, Topological Analysis, and Oxidation Catalytic Properties

作者：Gupta Samik; Kirillova Marina V; Guedes da Silva M Fatima C; Pombeiro Armando J L; Kirillov Alexander M

来源：Inorganic Chemistry, 2013, 52(15): 8601-8611.

DOI：10.1021/ic400743h

The reactions of [VO(acac)(2)] with bis(salicylaldehyde)-oxaloyldihydrazone (H4L) and an alkali metal carbonate M2CO3 (M = K, Na, Cs), in EtOH/H2O medium upon reflux, resulted in the generation of three new heterometallic V-v/M materials, namely the ID [(VO2)(2)(mu(4)-L){Na-2(mu-H2O)(2)(H2O)(2)}](n) (1), 2D [{V(mu-O)(2)}(2)(mu(4)-L){K-2(mu-H2O)(2)(H2O)(2)}](n) (2), and 3D ({V(mu-O)(mu(3)-O)]2(mu(8)-L){Cs-2(mu-H2O)(2)(H2O)(2)}(n) (3) coordination polymers. They were isolated as air stable solids and fully characterized by IR, UV-vis, H-1, and V-51 NMR spectroscopy, ESI-MS(), elemental, thermal, and single crystal X-ray diffraction analyses, the latter showing that 1-3 are constructed from the resembling [(VO2)2(mu(4/8)-L)](2-) blocks assembled by the differently bound aqua-metal [M-2(,mu-H2O)2(H2O)2](2+) moieties (M = Na, K, Cs). The main distinctive features of 1-3 arise from the different coordination numbers of Na (5), K (7), and Cs (9) atoms, thus increasing the complexity of the resulting networks from the ladder-like ID chains in 1 to double 2D layers in 2, and layer-pillared 3D framework in 3. The topological analysis of 2 disclosed a uninodal 4-connected underlying net with a rare kgm [Shubnikov plane net (3.6.3.6)/kagome pattern] topology, while 3 features a trinodal 4,7,8-connected underlying net with an unprecedented topology. Compounds 1-3 also show solubility in water (S-25 degrees C approximate to 4-7 mg mL(-1)) and were applied as efficient precatalysts for the homogeneous oxidation of cyclohexane by aqueous H2O 2 under mild conditions (50 C) in MeCN/H2O medium and in the presence of an acid promoter. Total yields (based on substrate) of cydohexanol and cyclohexanone up to 36% and turnover numbers (TONs) up to 5700 were achieved.

• 出版日期2013-8-5