Synthesis and Crystal Structure of a New Organic-inorganic Hybrid One-dimensional Polymer： [Zn（C8H23N5）]2（Pb3I10）

1 INTRODUCTION Recently, the organic-inorganic hybrid Ⅳa groupmetal halides with low-dimensional structure haveattracted much attention of chemists and physicistsdue to their particular properties and applications.For example, they are akin to “natural quantum-well”architectures and have tunable excitonic propertiesusually governed by the inorganic substructure andorganic component[1]; they have been applied assome technologically important materials, such assemiconductor materials in …     

Structure and Semiconducting Character of a Polymeric Iodoplumbate Coordination Complex

A new polymeric iodoplumbate complex [Zn(DMF)6][Pb2I6] 1 has been prepared and characterized by elemental analysis and single-crystal X-ray analysis. Its structure contains infinite iodoplumbate chains constructed by the [PbI5] subunit. EHT crystal orbital calculation and the experimental results show that this material is an unconventional semiconductor and the electrical character is associated with its structural feature.     

In situ Alkylation of 4,4'-Bipyridine in Hydrothermal Synthesis of an Iodoplumbate Inorganic-organic Hybrid with Fluorescence

A novel 1-D iodoplumbate hybrid,2(Pb3I9)3-·3(C14H18N2)2+ 1,has been hydrothermally synthesized and characterized by IR spectra,TGA and single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group P21/c,with a=12.057(2),b=14.024(3),c=24.742(5) ,β=90.48(3)°,V=4183.6(14)3,Z=4,R=0.0477 and wR=0.0800.The title compound consists of 1-D chains(Pb3I9)n3n-parallel to the [100] direction and stacks of alkylated 4,4'-bipyridium cations running along the [011] direction.Each anionic chain is surrounded by six arrays of alkylated 4,4'-bipyridium cations through extensive C-H…I atypical hydrogen-bonding interactions to afford an interesting 3-D supramolecular network.Significant fluorescent property of the compound was observed at room temperature.     

Polymeric Iodoplumbate Incorporating Copper Iodide Complex Cation Layer:Structure and Theoretical Study of a New Semi-conductive Hybrid:{[Cu(Ⅱ)(bipy)_2I][PbI_3](H_2O)_2}_n

A new iodoplumbate polymer incorporating copper iodide complex cation {[Cu(Ⅱ)(bipy)2I][PbI3](H2O)2}n 1(bipy = 2,2'-bipyridine) has been synthesized and structurally determined.It crystallizes in the triclinic system,space group P1 with a = 7.979(4),b = 14.538(11),c = 15.853(8),α = 110.77(2),β = 97.955(18),γ = 104.88(2)°,V = 1607.3(17)3,Z = 2,C20H16CuI4N4O2Pb,Mr = 1122.72,Dc = 2.320 g/cm3,F(000) = 1006,μ(MoKα) = 9.753,the final R = 0.0627 and wR = 0.1741 for 4846 observed reflections with Ⅰ 2σ(Ⅰ).Structural analysis indicates that 1 consists of 2-D {[Cu(Ⅱ)(bipy)2I]}nn+ cation layers(based on π-π interaction and hydrogen bonds) and [PbI3]nn-polyanions.The C-H···I hydrogen bonds between {[Cu(Ⅱ)(bipy)2I]}nn+ cation layers and [PbI3]nn-polyanions lead to the formation of an interesting 3-D network.Optical absorp-tion spectrum indicates that 1 is a semiconductor,which is further validated by DFT calculation.Its electronic structure is also discussed.     

Heterometallic iodoplumbates modified by copper(I) or silver(I) with viologens

Cu/Ag(I) were introduced into iodoplumbate systems to produce two new heterometallic iodoplumbates with viologen as templates, i.e. (PV)₂(Pb₂Cu₂I₁₀) (1) and [(BV)(Pb₂AgI₇)]_n (2) (PV²⁺ = propyl viologen, BV²⁺ = benzyl viologen), in which the common connection of PbI₆ units have been remarkably altered. In (PV)₂(Pb₂Cu₂I₁₀) (1), two PbI₆ octahedra are bridged by two CuI₄ tetrahedra via face-sharing to give a (Pb₂Cu₂I₁₀)^4? cluster, but the ternary one-dimensional polymeric (Pb₂AgI₇)_n^2n? of [(BV)(Pb₂AgI₇)]_n (2) is assembled from edge-sharing AgI₄ tetrahedra and PbI₆ octahedra. Their optical band gaps and fluorescence were also discussed. The absorption edges of haloplumbates could be engineered by introduction of suitable conjugated molecules as templates.     

原位合成苯并咪唑衍生物调控一维PbI_3~-盐的晶体结构和光学性质

以原位N-烷基化合成的苯并咪唑衍生物R2-bzim(R=H-,CH3-,C6H5CH2-;bzim=苯并咪唑)为模板,合成了3个含一维PbI3-盐的无机-有机杂化材料.X射线单晶衍射结果表明,随着模板剂尺寸的增大一维无机链由双链结构转变为单链结构.相对于体相PbI2,这些化合物有0.38～0.46eV的带隙蓝移,体现出比较强的量子限域效应.光致发光研究表明,通过模板剂的调控,3个化合物分别表现出绿、橙、黄光发射.     

Synthesis,Crystal Structure and Luminescent Property of a 2-D Hybrid Constructed from [Pb_2I_4] Subunits

A novel organic-inorganic hybrid compound, [Pb2I4（bipy）], （bipy = 4,4′-bipyridine）, was synthesized by self-assembly and its structure was determined by X-ray crystallography method The crystal belongs to the monoclinic system, space group P2 1/c with α = 4.4691（9）, b = 15.385（3）, c = 14.136（3） A, β = 93.75（3）°, V= 969.9（3） A^3, Mr = 1078.16, Dc= 3.692 g/cm^3, F（000） = 916, μ = 23.688 mm^-1, Z = 2, the final R = 0.0395 and wR = 0.0887 for 1557 observed reflections with I 〉 2σ（I）. The title compound presents a two-dimensional layer-like structure constructed from [PbI5N] octahedron and bis-bridging ligand 4,4′-bipyridine. The fluorescence of the title compound is also discussed in this communication.     

Iodoplumbate mit polymeren Anionen – Synthese und Kristallstrukturen von [Na3(OCMe2)12][Pb4I11(OCMe2)], (Ph4P)2[Pb5I12] und (Ph4P)4[Pb15I34(dmf)6]

Iodoplumbates with Polymeric Anions – Synthesis and Crystal Structures of [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)], (Ph₄P)₂[Pb₅I₁₂], and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] Reactions of PbI₂ with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 , (Ph₄P)₂[Pb₅I₁₂] 4 and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 contain one-dimensional infinite anionic chains of face- or edge-sharing PbI₆ or PbI₅L (L = acetone, DMF) octahedra. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 : Space group P1 (No. 1), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, α = 74.64(4), β = 70.40(4), γ = 85.24(4)°, V = 2071(2) · 10⁶ pm³; (Ph₄P)₂[Pb₅I₁₂] 4 : Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, β = 96.240(13)°, V = 6885(2) · 10⁶ pm³; (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 : Space group P2₁/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4) pm, β = 114.432(13)°, V = 9678(3) · 10⁶ pm³.     

A 3D Iodoplumbate Semiconducting Open Framework with Visible‐light‐induced Photocatalytic Performance

Employing in situ N‐alkylation of the conjugated compound 9,10‐bis(4‐pyridyl)anthracene (bpanth) as structure‐directing agent, a 3D inorganic‐organic hybrid iodoplumbate, [Me₂(bpanth)][Pb₄I₁₀] ( 1 ), was solvothermally prepared. The in situ N‐alkylation of bpanth with alcohols was investigated. 1 features a novel 3D open framework based on an interesting Pb₆I₂₄ cluster. UV/Vis spectroscopy analyses indicate that 1 is a potential semiconductor material with a narrow energy gap of 2.06 eV. It exhibits good catalytic activity in the visible‐light‐drived degradation of an organic dye. This work further illustrates that introducing conjugated organic molecules as templates is conducive to achieving semiconducting hybrid halometallates with narrow band gaps.