Synthesis and Structural Studies of Diorganotin(IV)-Based Coordination Polymers Bearing Silaalkylphosphonate Ligands and Their Transformation into Colloidal Domains

The contribution of silaalkylphosphonic acids Me3SiCH2P(O)(OH)(2) (1) and Me3SiC(CH3)(2)P(O)(OH)(2) (2) as ligands was demonstrated for the first time by the isolation of new diorganotin(IV) phosphonates Et2Sn{OP-(O)(OH)CH2SiMe3}(OSO2Me) (3), (Et2Sn)(6){O3PC-(CH3)(2)SiMe3}(4)(OSO2Me)(4) (4), and Et2Sn(O3PCH2SiMe3) (5). X-ray crystallographic studies of 1-4 are presented. The structures of 1 and 2 adopt extended motifs by virtue of P-OH center dot center dot center dot O=P-type hydrogen bonding interactions. The molecular structure of 3 is composed of a dimer formed by bridging hydrogen phosphonate groups, while the sulfonate group appended on each tin atom acts in a mu(2)-bridging mode to afford the formation of one-dimensional coordination polymer featuring alternate eight-membered [-Sn-O-P-O-](2) and [-Sn-O-S-O](2) rings. The asymmetric unit of 4 is composed of two crystallographically unique trinuclear tin phosphonate clusters with a Sn-3(mu(3)-PO3)(2) core linked together by coordinative association of a mu(2)-sulfonate group, while the remaining sulfonates are involved in the construction of a two-dimensional self-assembly. The identity of 1-5 in solution was established by IR and multinuclear (H-1, C-13, P-31, Sn-119) NMR spectroscopy. The presence of silaalkyl group in 5 imparts unusual solubility in hydrocarbon, aromatic, and ether solvents. As a consequence, the formation of colloidal particles of 5 featuring rodlike morphology was achieved by ultrasonication of a solution in ethanol-chloroform mixture.