TY - JOUR
T1 - Dinuclear platinum complexes with hydrogen-bonding functionality
T2 - Noncovalent assembly of nanoscale cyclic arrays
AU - Gianneschi, Nathan C.
AU - Tiekink, Edward R.T.
AU - Rendina, Louis M.
PY - 2000/9/6
Y1 - 2000/9/6
N2 - The preparation and solution behavior of a series of novel, dinuclear organoplatinum(II) complexes of nicotinic acid 3 and 4, isonicotinic acid 5, and nicotinamide 6 are reported. For 3 and 4, comprehensive 1H NMR titration studies demonstrate their spontaneous self-association to afford discrete, hydrogen-bonded aggregates in CD2Cl2 solution at 298 ± 0.1 K. For 3, the titration data are consistent with the formation of a nanoscale cyclic entity (3)3 which, despite rise presence of bulky PPh3 ligands, is strongly favored in solution (K3 = 1.99 x 104 ± 7.89 x 102 mol-2 dm6). Complex 4 aggregates to form a cyclic dimer (4)2 with K2 = 98.2 ± 1.1 mol-1 dm3, and complexes 5 and 6 appear to afford oligomeric (or polymeric) aggregates. The X-ray crystal structure of 6 shows the dications associate to form corrugated chains connected by hydrogen bonds. This work demonstrates that the noncovalent assembly of multimeric cyclic arrays with nanoscale dimensions from simple diplatinum(II) complexes is feasible in nonaqueous solution.
AB - The preparation and solution behavior of a series of novel, dinuclear organoplatinum(II) complexes of nicotinic acid 3 and 4, isonicotinic acid 5, and nicotinamide 6 are reported. For 3 and 4, comprehensive 1H NMR titration studies demonstrate their spontaneous self-association to afford discrete, hydrogen-bonded aggregates in CD2Cl2 solution at 298 ± 0.1 K. For 3, the titration data are consistent with the formation of a nanoscale cyclic entity (3)3 which, despite rise presence of bulky PPh3 ligands, is strongly favored in solution (K3 = 1.99 x 104 ± 7.89 x 102 mol-2 dm6). Complex 4 aggregates to form a cyclic dimer (4)2 with K2 = 98.2 ± 1.1 mol-1 dm3, and complexes 5 and 6 appear to afford oligomeric (or polymeric) aggregates. The X-ray crystal structure of 6 shows the dications associate to form corrugated chains connected by hydrogen bonds. This work demonstrates that the noncovalent assembly of multimeric cyclic arrays with nanoscale dimensions from simple diplatinum(II) complexes is feasible in nonaqueous solution.
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U2 - 10.1021/ja994483m
DO - 10.1021/ja994483m
M3 - Article
AN - SCOPUS:0033832740
SN - 0002-7863
VL - 122
SP - 8474
EP - 8479
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 35
ER -