Solvothermal syntheses, crystal structures, and characterizations of a series of one-dimensional organic-containing gallium polyselenides

Five new gallium polyselenides, namely [1,3-pdaH2][Ga2Se2(Se2)(Se3)] (1) (1,3-pda = 1,3-diaminopropane), [1,4-bdaH2][Ga2Se3(Se2)] (2) (1,4-bda = 1,4-diaminobutane), [Me2NH2]2[Ga2Se2(Se2)2] (3), α-[AEPH]2[Ga2Se2(Se2)2] (4) (AEP = N-(2-aminoethyl)piperazine), and β-[AEPH]2[Ga2Se2(Se2)2] (5), have been synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction, thermogravimetric analyses and solid-state UV-Vis diffuse reflectance spectroscopy. Compound 1 features a one-dimensional (1D) chain of [Ga2Se2(Se2)(Se3)]n2n− constructed by alternating five-membered rings [Ga2Se(Se2)] and six-membered rings [Ga2Se(Se3)] sharing Ga atoms. Compound 2 features a 1D chain of [Ga2Se3(Se2)]n2n− built from alternating four-membered rings [Ga2Se2] and five-membered rings [Ga2Se(Se2)] joined at Ga atoms. Compounds 3, 4 and 5 feature a 1D-[Ga2Se2(Se2)2]n2n− chain made up by fusing five-membered rings [Ga2Se(Se2)] at Ga atoms. The polymorphic noncentrosymmetric compound 4 and centrosymmetric compound 5 were isolated at different temperatures under solvothermal conditions. The absorption edges reveal band gaps of 2.08 eV for 1, 2.32 eV for 2, 2.07 eV for 3, 1.93 eV for 4 and 2.10 eV for 5, respectively. Their thermal stabilities were investigated viathermogravimetric analysis (TGA).

[1]  A. Powell,et al.  Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: A new one-dimensional indium selenide , 2011 .

[2]  Hongming Yuan,et al.  Synthesis and Characterization of Ethylenediammonium Molybdenum Thiocomplex [H3NCH2CH2NH3][Mo3S13] , 2010 .

[3]  J. Dai,et al.  Structural Study of Organic−Inorganic Hybrid Thiogallates and Selenidogallates in View of Effects of the Chelate Amines , 2008 .

[4]  P. Vaqueiro,et al.  Three-dimensional gallium sulphide open frameworks , 2007 .

[5]  P. Vaqueiro From one-dimensional chains to three-dimensional networks: solvothermal synthesis of thiogallates in ethylenediamine. , 2006, Inorganic chemistry.

[6]  P. Vaqueiro Solvothermal synthesis and characterisation of new one-dimensional indium and gallium sulphides: [C10N4H26]0.5[InS2] and [C10N4H26]0.5[GaS2] , 2006 .

[7]  A. Powell,et al.  Methylammonium antimony sulfide. , 2005, Acta crystallographica. Section C, Crystal structure communications.

[8]  B. Wang,et al.  Three-dimensional frameworks of gallium selenide supertetrahedral clusters. , 2004, Angewandte Chemie.

[9]  M. Kanatzidis,et al.  The One‐dimensional Polyselenide Compound CsGaSe3 , 2003 .

[10]  Xianhui Bu,et al.  Nonaqueous synthesis and selective crystallization of gallium sulfide clusters into three-dimensional photoluminescent superlattices. , 2003, Journal of the American Chemical Society.

[11]  K. Vidyasagar,et al.  Molten flux synthesis, single crystal X-ray structure and ion-exchange properties of the first polythiogallate, CsGaS3 , 2002 .

[12]  X. Chen,et al.  Rb(4)Hg(5)(Te(2))(2)(Te(3))(2)Te(3), [Zn(en)3](4)In(16)(Te2)4(Te3)Te22, and K2Cu2(Te2)(Te3): novel metal polytellurides with unusual metal-tellurium coordination. , 2001, Inorganic chemistry.

[13]  R. Blachnik,et al.  [Ga(en)3][Ga3Se7(en)] · H2O: Ein Galliumchalkogenid mit Ketten aus [Ga3Se6Se2/2(en)]3–‐Bicyclen , 1999 .

[14]  M. Kanatzidis,et al.  Counterion Effects in Pd Polyselenides: Evolution from Molecular to Three-Dimensional Framework Structures , 1998 .

[15]  R. Haushalter,et al.  SYNTHESIS AND CHARACTERIZATION OF TWO NEW TELLUROINDATES : K6IN2TE6.4C2H8N2 AND (PH4P)2IN2TE6 , 1997 .

[16]  T. Emge,et al.  New Type of Polymeric Indium Tellurides: Low-Temperature Synthesis and Structure Characterization of [M(en)(3)]In(2)Te(6) (M = Fe, Zn) and alpha- and beta-[Mo(3)(en)(3)(&mgr;(2)-Te(2))(3)(&mgr;(3)-Te)(&mgr;(3)-O)]In(2)Te(6). , 1997, Inorganic chemistry.

[17]  J. Ibers,et al.  Different Products from the Chemical and Electrochemical Reduction of “HgSe2”: [K(2.2.2-cryptand)]2[HgSe2] and [PPh4]2[Hg(Se4)2]·en , 1997 .

[18]  Christopher J. Warren,et al.  One-Dimensional Mercury Telluride Polymers: Synthesis and Structure of (Et4N)2Hg2Te4 and (Me4N)4Hg3Te7.cntdot.0.5en , 1994 .

[19]  M. Kanatzidis,et al.  Coordination chemistry of heavy polychalcogenide ligands , 1994 .

[20]  M. Kanatzidis,et al.  Synthesis of [Tl4Se16]4−: a novel tetranuclear Tl3+ polyselenide , 1993 .

[21]  M. Kanatzidis,et al.  Polyselenide chemistry of indium and thallium in dimethylformamide, acetonitrile, and water. Syntheses, structures, and properties of the new complexes [In2(Se4)4(Se5)]4-, [In2Se2(Se4)2]2-, [In3Se3(Se4)3]3-, and [Tl3Se3(Se4)3]3- , 1993 .

[22]  M. Kanatzidis,et al.  Syntheses and characterization of the new homoleptic indium-polysulfide complexes [In2S27]4-, [In2S14]2-, and [In2S16]2- , 1993 .

[23]  M. Kanatzidis,et al.  Syntheses and characterization of the first thallium polysulfide anions , 1993 .

[24]  M. Kanatzidis,et al.  Open Framework Structures Based on Sex2– Fragments: Synthesis of (Ph4P)[M(Se6)2] (M = Ga, In, TI) in Molten (Ph4P)2Sex , 1992, Science.

[25]  G. Gattow,et al.  Untersuchungen über Polythiocuprate(I) [Cu(Sx)]−. 3. Kristallstruktur von [H3NC2H4NH3][Cu(S5)]2 · 4 H2O , 1991 .

[26]  M. Kanatzidis,et al.  Isolation of a sulphur-rich indium polysulphide complex containing two different Sx2- ligands. Synthesis and structure of [InS10Br]2- , 1991 .

[27]  J. Kolis Coordination Chemistry of Polychalcogen Anions and Transition Metal Carbonyls , 1990 .

[28]  A. Hofmann,et al.  Na5InTe4 und Na5In2Te6 — Erste Beispiele für Neso-sowie Ditelluro-verbrückte Inotelluroindate/Na5InTe4 and Na5In2Te6 — First Examples of Neso-and Ditelluro-Bridged Inotelluroindates , 1990 .

[29]  M. Springford The Luminescence Characteristics of Some Group III-VI Compounds , 1963 .