A new class of solid-state networks containing covalent linkages between a metal and organic spacer has been established through the treatment of M(OR)4 (M = Ti, Zr, V) with excess dihydroxyaromatics ((HO)2Ar) in various solvents (L). Some structural control--a paramount goal--has been achieved. In weak donor solvents, 3-D materials are created (X-ray): 1) Ti(OiPr)4, quinone, Et2O -> [Ti2(f-1,6-OC6H4O)2(f-1,6-OC6H4OH)2(f-OC6H4OH)2] (1); 2) Ti(OiPr)4, quinone, MeCN/H2O -> [Ti2(f-1,6-OC6H4O)2(f-1,6:eta-2,eta1-OC6H4O)2(OH2)2.(H2O)2.(HOC6H4OH).2( (2); 3) Ti(OiPr)4, 2,7-(OH)2-napthalene, Et2O -> [Ti2(f-1,7-OC10H6O)2(f-1,7:eta-2,eta-1-OC10H6OH)2(O-iPr)2] (3). In strong donor solvents, 2-D complexes are prepared (X-ray): 1) Ti(OiPr)4, quinone,py -> [cis-Ti(f-1,6-OC6H4O)2(py)2] (4a); 2) Ti(OiPr)4, quinone, py -> [trans-Ti(f-1,6-OC6H4O)2(py)2.py] (4b); Ti(OiPr)4, resourcinol, L (py, 4-Ph-py -> [trans-Ti(f-1,5-OC6H4O)2L2] (5). With long spacers and good donors, the dimensionality can reduce further, as shown by the 1-D ladder [cis-Ti(f-1,7-OC10H6O)2(py)2] (6). Vanadium analogues of 1, 4b, and 5 have been prepared. Approximately 100 new compounds have been cleanly prepared from various M, spacer and L, but X-ray quality crystals are difficult to obtain due to insufficient size (<10-20 fm).
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