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ABSTRACT: This work focuses on the investigation of targeting homometallic mixed-valence copper(I/II) Schiff base coordination polymers (CPs) via a proposed synthetic strategy, namely, in situ immobilization of metalloligands. We have designed and synthesized three structurally related isomeric Schiff base ligands, all of which contain chelating and bridging sites and, accordingly, obtained two distinctly shaped metalloligands, namely, [Cu(L1)(2)] (1) and [Cu(L3)(2)] (3a) [HL = pyridinecarbaldehyde isonicotinoyl hydrazone]. By introducing cyanide-bridging spacers to the one-pot solvothermal reactions, the copper(II) Schiff base metalloligands 1 and 3a are in situ immobilized in two diverse mixed-valence copper(I/II) Schiff base CPs, namely, [Cu(4)(CN)(3)(L1)(2)](n) (4) and {[Cu(4)(CN)(3)(L3)(2)].2.5H(2)O}(n) (6). Additionally, the formation of three unexpected CPs, namely, [Cu(L3)(2)](n) (3b), [Cu(L2)(2)](n) (2), and [Cu(2)(CN)(2)(HL2)](n) (5), indicates that the coordinating sites of the ligands and the symmetry of the metalloligands should be taken into consideration in this synthetic algorithm.
Inorganic Chemistry 02/2009; 48(4):1433-41. · 4.60 Impact Factor
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ABSTRACT: Solvothermal reactions of CuII salts and 3,5-bis(4-pyridyl)pyrazole (HL) under various conditions gave three different types of crystalline compound, namely [Cu2(Cu5L6)]BF(4).5 H2O (1 a), [Cu2(Cu5L6)]ClO(4).5 H2O (1 b), and [Cu7(CN)2(Cu5L6)2][BF4]3 (2). 1 a and b were obtained in ethanol and NH3.H2O, whereas 2 was obtained in methanol and NH3.H2O. The three complexes were constructed by incorporating new pentanuclear copper(I) pyrazolate bis(triple helical) cluster helicates (Cu5L6) as the second building units (SBUs), in which as many as twelve 4-pyridyl N atoms are available for further coordination and construction of high-connectivity topological networks. In 1 a and b, seven 4-pyridyl N atoms are linked to three three-coordinated CuI atoms and four four-coordinated CuI atoms, which results in 3,4,7-connected networks. In 2, as many as eleven 4-pyridyl N atoms coordinate to eleven CuI atoms, which results in a 4,10-connected topological network. The increasing connectivity of the cluster nodes in 2 is closely related to the in situ-formed CN- anion bridge around the periphery of the pentanuclear cluster helicates. The luminescenct properties of these compounds were also investigated.
Chemistry 09/2008; 14(29):8916-21. · 5.93 Impact Factor
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Angewandte Chemie International Edition 08/2008; 47(34):6371-4. · 13.45 Impact Factor
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Angewandte Chemie International Edition 02/2008; 47(9):1711-4. · 13.45 Impact Factor
