Framework coordination polymers of tetra(4-carboxyphenyl)porphyrin and lanthanide ions in crystalline solids.

Targeted synthesis of framework coordination polymers was achieved by reacting meso-tetra(4-carboxyphenyl)porphyrin with common salts of lanthanide metal ions. The large size, high coordination numbers and strong affinity for oxo ligands of the latter, combined with favourable hydrothermal reaction conditions in acidic environments, allowed the formation of open three-dimensional single-framework architectures in which the tetra-dentate porphyrin units are inter-coordinated by multinuclear assemblies of the bridging metal ions, which serve as construction pillars, into infinite architectures. Three different modes of coordination polymerisation were characterized by single-crystal X-ray diffraction.

Porphyrin framework solids. Synthesis and structure of hybrid coordination polymers of tetra(carboxyphenyl)porphyrins and lanthanide-bridging ions.

New types of porphyrin-based framework solids were constructed by reacting meso-tetra(3-carboxyphenyl)porphyrin and meso-tetra(4-carboxyphenyl)metalloporphyrins with common salts of lanthanide metal ions. The large size, high coordination numbers and strong affinity for oxo ligands of the latter, combined with favorable hydrothermal reaction conditions, allowed the formation of open three-dimensional single-framework architectures by coordination polymerization, in which the tetradentate porphyrin units are intercoordinated by multinuclear assemblies of the bridging metal ions. The latter serve as construction pillars of the supramolecular arrays, affording stable structures.

Crystal engineering of urea alpha-network via I...O2N synthon and design of SHG active crystal N-4-iodophenyl-N'-4'-nitrophenylurea.

Crystalline nitrodiphenyl ureas adopt the N-H...