Structural diversity and retro-crystal engineering analysis of iodometalate hybrids

With guidance from retro-crystal engineering, iodometalate structures based on MI6 octahedra of group 14 (M = Sn(II), Pb(II)) and group 15 (M = Sb(III) and Bi(III)) are analysed. The criterion of I/M ratio, with the function of indicating the degree of condensation of octahedra in inorganic networks and the average charge density at the organic–inorganic interface, is introduced to classify all of the iodometalate networks, resulting in an easy and clear way to identify isomers with different dimensionalities. Of all iodometalates, the 2D M(II)I4 anion derived from the perovskite network is special since it can be easily stabilized by a range of common organic cations. We provide here the up-to-date progress in this extensively studied field, focusing on crystal engineering of hybrids in the aim of getting materials with a reduced band gap. Relationships between the molecular layouts of cationic entities and the structures of several non-perovskite anionic networks, focusing on the organic–inorganic interface, are highlighted. Distinct dependences between different types of cations and different types of anions are revealed, although it is still unfeasible to apply them in the actual control, design, or prediction of specific hybrid structures

A Switchable NLO Organic-Inorganic Compound Based on Conformationally Chiral Disulfide Molecules and Bi(III)I5 Iodobismuthate Networks

A novel organic-inorganic hybrid based on cystamine and BiI5chains is prepared. Due to the flexibility of the disulfide molecules in the structure, single crystals or crystalline thin films of this hybrid undergo a reversible acentric-to-centric structural transition at moderate conditions (T = 36.8 °C). This makes the title compound an excellent candidate for temperature controlled SHG or THG switches

Reactivity of CuI and CuBr toward Dialkyl Sulfides RSR: From Discrete Molecular Cu 4

The 1D coordination polymer (CP) [(Me2S)(3){Cu-2(mu-I)(2)}](n) (1) is formed when CuI reacts with SMe2 in n-heptane, whereas in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me2S)(3){Cu-4(mu-I)4}](n) (2) containing flower-basket Cu4I4 units. The reaction product of CuI with MeSEt is also solvent-dependent, where the 1D polymer [(MeSEt)(2){Cu-4(mu(3)-I)(2)(mu(2)-I)(2)}(MeCN)(2)](n) (3) containing stepped-cubane Cu4I4 units is isolated in MeCN. In contrast, the reaction in n-heptane affords the 1D CP [(MeSEt)(3){Cu-4(mu(3)-I)4}](n) (4) containing closed-cubane Cu4I4 clusters. The reaction of MeSPr with CuI provides the structurally related 1D CP [(MeSPr)(3){Cu-4(mu(3)-I)4}](n) (5), for which the X-ray structure has been determined at 115, 155, 195, 235, and 275 K, addressing the evolution of the metric parameters. Similarly to 4 and the previously reported CP [(Et2S)(3){Cu-4(mu(3)-I)4}](n) (Inorg. Chem. 2010, 49, 5834), the 1D chain is built upon closed cubanes Cu-4(mu(3)-I)4 as secondary building units (SBUs) interconnected via mu-MeSPr ligands. The 0D tetranuclear clusters [(L)4{Cu-4(mu(3)-I)4}] [L = EtSPr (6), Pr2S (7)] respectively result from the reaction of CuI with EtSPr and n-Pr2S. With i-Pr2S, the octanuclear cluster [(i-Pr2S)(6){Cu-8(mu(3)-I)(3)}(mu(4)-I)(2)}] (8) is formed. An X-ray study has also been performed at five different temperatures for the 2D polymer [(Cu3Br3)(MeSEt)(3)](n) (9) formed from the reaction between CuBr and MeSEt in heptane. The unprecedented framework of 9 consists of layers with alternating Cu(mu(2)-Br)(2)Cu rhomboids, which are connected through two mu-MeSEt ligands to tetranuclear open-cubane Cu4Br4 SBUs. MeSPr forms with CuBr in heptane the 1D CP [(Cu3Br3)(MeSPr)(3)](n) (10), which is converted to a 2D metalorganic framework [(Cu5Br5)(mu(2)-MeSPr)(3)](n) (11) incorporating pentanuclear [(Cu-5(mu(4)-Br)(mu(2)-Br)] SBUs when recrystallized in MeCN. The thermal stability and photophysical properties of these materials are also reported