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]·Hphen·3HDMA·8H2O (Mp-InS-4) (DMA = dimethylamine) is a 1-D straight chain. Compounds [M(phen)3]4[In20S37]·6Hphen·4H2O (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]·2Hphen·2HDMA·3H2O (Mp-InS-7) shows a zigzag 1-D structure. We find that the reaction time is an important factor in assembling of the T3 clusters. 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.