title: A 3D hybrid praseodymium-antimony-oxochloride compound: single-crystal-to-single-crystal transformation and photocatalytic properties.
abstract: A 3D organic-inorganic hybrid compound, (2-MepyH)3[{Fe(1,10-phen)3}3][{Pr4Sb12O18(OH)Cl(11.5)}(TDC)(4.5)({Pr4Sb12O18(OH)Cl(9.5)} Cl)]·3(2-Mepy)·28H2O (1; 2-Mepy=2-methylpyridine, 1,10-phen=1,10-phenanthroline, H2TDC=thiophene-2,5-dicarboxylic acid), was hydrothermally synthesized and structurally characterized. Unusually, two kinds of high-nuclearity clusters, namely [(Pr4Sb12O18(OH)Cl11)(COO)5](5-) and [(Pr4Sb12O18(OH)Cl9)Cl(COO)5](4-), coexist in the structure of compound 1; two of the latter clusters are doubly bridged by two μ2-Cl(-) moieties to form a new centrosymmetric dimeric cluster. An unprecedented spontaneous and reversible single-crystal-to-single-crystal transformation was observed, which simultaneously involved a notable organic-ligand movement between the metal ions and an alteration of the bridging ion in the dimeric cluster, induced by guest-release/re-adsorption, thereby giving rise to the interconversion between compound 1 and the compound (2-MepyH)3[{Fe(1,10-phen)3}3][{Pr4Sb12O18(OH)Cl(11.5)}(TDC)4({Pr4Sb12O18Cl(10.5)(TDC)(0.5)(H2O)(1.5)}O(0.5))]·25H2O (1'). The mechanism of this transformation has also been discussed in great detail. Photocatalytic H2-evolution activity was observed for compound 1' under UV light with Pt as a co-catalyst and MeOH as a sacrificial electron donor.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (P.R. China), Fax: (+86) 591-83793727; University of Chinese Academy of Sciences, Beijing, 100049 (P.R. China).
authors.forename: Guo-Dong
authors.initials: GD
authors.lastname: Zou
authors.forename: Gui-Gang
authors.initials: GG
authors.lastname: Zhang
authors.forename: Bing
authors.initials: B
authors.lastname: Hu
authors.forename: Jian-Rong
authors.initials: JR
authors.lastname: Li
authors.forename: Mei-Ling
authors.initials: ML
authors.lastname: Feng
authors.forename: Xin-Chen
authors.initials: XC
authors.lastname: Wang
authors.forename: Xiao-Ying
authors.initials: XY
authors.lastname: Huang
keywords: cluster compounds; dimerization; organic-inorganic hybrid composites; photolysis; praseodymium