基于2-羧乙基苯基次膦酸的超分子异构现象和特殊氢键的分析-有机化学专业论文.docxVIP

Abstract 2Among the broad family of metal–organic coordination polymers, carboxylate, phosphonate and sulfonate are the most widely used ligands for moderate or strong ligation, whereas phosphinate (R1R2PO -) has rarely been employed for the construction of coordination polymers. Phosphinate can be viewed as a tetrahedra (P atom in the center, four vertices are occupied by two O atoms and two C atoms). The oxygen atom of phosphonic acid can not only show strong coordination abilities, but also be apt to form strong hydrogen bond interactions. Compared with 2 the mono-organic-group-attached carboxylate or phosphonate moieties, the phosphinate group is further bonded to an additional organic group, which can allow a better modulation of the structure of the resultant metal complexes. In our current studies, we selected (2-carboxyethyl)(phenyl)phosphinic acid (H2L) as the main ligand, and 1,10-phenanthroline (phen) as the auxiliary ligand. Our research efforts afforded a series of a novel metal phosphinates, namely, [Mn(L)(phen)(H2O)]·2(H2O) (1), [Mn(L)(phen)(H2O)] (2), [Cu(L)(phen)(H2O)]·3(H2O) (3), [Cd(L)(phen)] (4), [Cd(L)(phen)]·3(H2O) (5), [Cd(L)(phen)]·13/6(H2O) (6), of which 1 and 2, as well as 4, 5 and 6, can be regarded as isomers, and 3 bears a strong structural analogy to 1, although the metal species in them are different. 1 and 3 show discrete dimer structures, while 2, 4, 5 and 6 feature different double-chain arrays. The addition of strong base such as sodium hydroxide or potassium hydroxide to the aqueous solution of (2-carboxyethyl)(phenyl)phosphinic acid afforded two novel monovalent metal carboxylate–phosphinates, namely, NaH(Ph-PO2-C2H4-COOH)2 (7) and [KH(Ph-PO2-C2H4-COOH)2]·H2O (8). The former shows a layer architecture while the latter features a chain array. Compounds 7 and 8 containing short, symmetric or almost symmetric O···H···O hydrogen bonds. Through the studies on the supramolecular isomerism and hydrogen bo