Structure and Optical Property of a New 1D Iodoplumbate Hybrid Directed by in situ Synthesized Asymmetrical N-benzyl-1,4-diazabicyclo 2.2.2 octane

摘要

Simple solvothermal reaction of PbI2,1,4-diazabicyclo[2.2.2]octane and benzyl alcohol in the presence of HI acid creates a new organically templated iodoplumbate hybrid:[(N-Bz-DABCO)(PbI3)]n (1,N-Bz-DABCO+ =N-benzyl-l,4-diazabicyclo[2.2.2]octane).Compound 1 crystallizes in orthorhombic space group P212121 with a =20.044(9),b =8.002(3),c =12.345(5) (A),V=1980.1(14) (A)3,Z =4,C13H19N2PbI3,Mr =791.19,Dc =2.654 g/cm3,F(000) =1408,μ(MoKa) =13.189 mm-1,the fmal R =0.0303 and wR =0.0849 for 3777 observed reflections (Ⅰ ＞ 2σ(Ⅰ)).Compound 1 contains one-dimensional anionic [PbI3]nn-chains that are enclosed into the cationic channel formed from the N-benzyl-l,4-diazabicyclo[2.2.2]octane.Noteworthy,compared with common symmetrical N,N'-dialkyl-DABCO2+ cations,in-situ formed asymmetrical N-monoalkyl-DABCO+ cation is first used as structure directing agents/templating agents in the haloplumbate system,finally leading to the occurrence of noncentrosymmetric feature in compound 1.In addition,UV-Vis absorption spectrum analysis reveals that compound 1 is a potential semiconductor material with energy gap of 2.80 eV.