A photochromic inorganic-organic hybrid based on in situ generated MV(2+) cation (MV(2+) = methyl viologen = N,N'-dimethyl-4,4'-bipyridinium) has been obtained, in which a vagarious partial photochromic phenomenon together with its photoluminescence modulation properties are reported for the first time in the inorganic-organic hybrids.

1,10-Phenanthroline (phen) and monoprotonated methylamine molecules were used as a novel cotemplate to direct the formation of a new inorganic-organic hybrid selenidostannate, (CH(3)NH(3))(4)(Sn(2)Se(6))·6phen (1); while the utilization of three types of transition-metal (TM) phen complex cations with the TM/phen ration of 1:1, 1:2, and 1:3 as structure directors affords {[Mn(phen)(2)](2)(μ(2)-Sn(2)Se(6))}·H(2)O (2a), {[Fe(phen)(2)](2)(μ(2)-Sn(2)Se(6))} (2b), {[Mn(phen)](2)(μ(4)-Sn(2)Se(6))}(n) (3), {[Mn(phen)(2)](Sn(2)Se(5))}(n) (4), and [Fe(phen)(3)](n)(Sn(3)Se(7))(n)·1.25nH(2)O (5). These compounds show diverse structures with the selenidostannate anions varying from discrete, μ(2)- and μ(4)- (Sn(2)Se(6))(4-) anions, to one-dimensional (1-D) (1)(∞)(Sn(2)Se(5)(2-)) anionic chains, and two-dimensional (2-D) extended (2)(∞)(Sn(3)Se(7)(2-)) anionic layers, demonstrating different structure-directing abilities of the cotemplate and the three types of TM phen complex cations. This work clearly indicates that the approach of modifying the number of the free coordination sites of unsaturated TM phen complex cations is very exciting as a way to synthesize novel hybrid chalcogenidometalates. Of particular interest, the present compounds exhibit interesting optical properties that reflect the combined effects of both photoluminescence-active organic components and semiconducting inorganic chalcogenidometalate anionic networks.

A 3D metal-organic framework (MOF), [Zn(BPHY)(SA)]n (1; BPHY = 1,2-bis(4-pyridyl)hydrazine, H2SA = succinic acid), which crystallizes in a noncentrosysmmetric space group (Cc), has been solvothermally obtained and testified to be a good nonlinear-optical material with the largest second-harmonic-generation response among the known MOFs based on sysmmetric ligands and high stability. Ultraviolet-to-visible tunable emission for 1 is observed.