As most of the chalcogenidometalate anions are well-known electron-rich systems, design and preparation of ion pair compounds, by integrating an organic acceptor (A) with an inorganic chalcogenidometalate donor (D), are an attractive strategy to obtain new functional materials. We report herein the single-crystal structures and properties of three new ion pair charge-transfer (IPCT) compounds by incorporating thiogermanates with methylviologen (MV(2+), N,N'-dimethyl-4,4'-bipyridinium dication), [MV]2Ge4S10·xSol (Sol = solvent). Sharp and fast solvent-induced color changes and switchable fluorescence emission are observed for the compounds. The weak interactions that relate to the solvent and ions in the structures are likely the key points to modulate the cation-anion charge-transfer. A photocurrent response is observed for the photoelectric system of the IPCT compound upon repetitive switching of light on and off.

Four new indium chalcogenide compounds 1-4 were prepared by a similar solvothermal synthetic method in 1,2-diaminocyclohexane (dach) medium with or without the auxiliaries of germanium oxide or ionic liquid 1-butyl-3-methyl imidazolium bromide. Among them, two unusual polymeric structures assembled by Tn clusters were found. The anion of {H 2 dach? [Ni(dach) 3 ]?[In 12 S 20 (dach) 2 ]?3H 2 O} n (1) is a threedimensional framework assembled by T3 clusters, in which the linkage is a unique In 4 (dach) 4 S 6 cluster. The anion of {(Hdach) 2 ?[Co(dach) 3 ] 4 ?[In 16 Co 4 S 37 ]?dach?5H 2 O} n (3) is an unusual two-dimensional framework assembled by T4 clusters, in which the T4 clusters are linked by (S 3 ) 22 polysulfide ion. The structures of the other two new compounds are known, and they are {[Ni(dach) 3 ]?[In 2 S 4 ]?3H 2 O} n (2) and{(Hdach) 4 ?[Co(dach) 3 ] 6 ?{[In 16 Co 4 S 34 ] 2 [Co(dach) 2 ] 3 }?6H 2 O} n (4). The auxiliaries play an important role in the structural assembly of the Tn clusters, mainly due to their effects on acidity of the reaction system and solubility of the reactants or products.

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