Indium-Sulfur Supertetrahedral Polymers Integrated with [M(phen)3]2+ Cations (M = Ni and Fe)

A series of supertetrahedral polymers of chalcogenometalates (T3 cluster compounds) integrated with M-phen complexes (phen =1,10-phenanthroline; M = Ni, Fe) was prepared by a similar solvothermal technique. Compound [Fe(phen)(3)](4)[H4In20S38]center dot Hphen center dot 3HDMA center dot 8H(2)O (Mp-InS-4) (DMA = dimethylamine) is a 1-D straight chain. Compounds [M(Phen)(3)](4)[In20S37]center dot 6Hphen center dot 4H(2)O (M = Ni, Mp-InS-5; Fe, Mp-InS-6) are the first reported 2-D Tn polymers integrated with complex cations of [M(phen)(3)](2+). Compound (Ni(phen)(3)](4)-[H4In20S38]center dot 2Hphen center dot 2HDMA center dot 3H(2)O (Mp-InS-7) shows a zigzag 1-D structure. We find that the reaction time is an important factor in assembling of the T3 dusters. Prolonging the reaction time seems favorable to the higher condensed phases (from 0-D to 2-D). However, a longer reaction time resulted in the crack of 2-D structure. Integrating M-phen complex cations with the chalcogenido anions can improve absorption of the materials in the visible range due to the charge transfers within the cations or between cations and anions.