Arylphosphonic acid esters as bridging ligands in coordination polymers of bismuth

The reaction of the arylphosphonic acid esters 4,4′-[(i-PrO)2P(O)]C6H4C6H4[P(O)(Oi-Pr)2] (L1), 1,3,5-[(i-PrO)2P(O)]3C6H3 (L2), and 5-t-Bu-1,3-[(i-PrO)2P(O)]2C6H3 (L3), respectively, with bismuth halides BiX3 (X=Cl, Br, I) gave seven novel bismuth coordination polymers that have been characterized by single-crystal X-ray diffraction analysis. The solid-state structures of [(BiCl3)(L1)] (1), [(BiBr3)(L1)]·0.25CH3CN (2·0.25CH3CN), [(BiI3)2(L1)]·0.25CH3CN (3·0.25CH3CN), [(BiCl3)(L2)] (4), [(BiCl3)2(L2)] (5), [(BiBr3)2 (L2)]·CH3CN (6·CH3CN), and [(BiCl3)(L3)] (7) are presented. Thermal analysis of [(BiCl3)2(L2)] (5) is indicative of a conversion of the complexes into a bismuth phosphonate by complete i-PrX elimination, whereas for [(BiBr3)2(L2)] (6), elimination of i-PrBr and BiBr3 is assumed. Compounds 1–3 form one-dimensional coordination polymers, whereas two-dimensional networks are observed for compounds 4–7.