Syntheses,Structures And Properties Of Pb(Cu)/I Coordination Compounds

Organic-inorganic hybrid complexes which possess excellent properties of both organic and inorganic materials were widely used in optical communications,photoluminescence/electroluminescent materials,semiconductor integrated circuits,photovoltaic materials,biomedicine and many other fields.Therefore,tremendous research has been performed on the Pb(Cu)/I complexes with novel structures and specific functions.In this paper,ten complexes have been successfully synthesized by introducing five kinds of organic ligands and two kinds of hetero-metals into Pb(Cu)/I framework using facile solvothermal and the solution method.In this article,2,2'-bipyridine(bipy),1,2-(4-pyridyl)-ethylene(dpe),1,10-phenanthroline(phen),o-diaminobenzene(OPD),and N,N-dimethylformamide(DMF)were used as organic ligands for preparing 10 novel Pb(Cu)/I complexes,which were listed as follows:Compounds 1 and 2 were prepared by solution method.Two kinds of one-dimensional chain-like [MLn]·[Pbx Xy] type organic-inorganic hybrid hetero-metallic complexes were formed by complexing hetero-metallic ions(Cu,Ni)with ligands(DMF,OPD).The cationic template is bound to the Pb/I anion framework by weak hydrogen bond.Compounds from 3 to 6 formed the network framework of Pb/I/Cu inorganic hybrid complex,which are of great novelty even until now.Among them,the compounds from 3 to 5 directly attached the hetero-metallic ions to the Pb/I inorganic frameworks through the ligand,and each component has strong covalent bond interaction.It is worth mentioning that the Cu atoms in compound 5 have a mixedvalence of both Cu I and Cu II,which has not been reported in M/X systems.In the compound 6,the hetero-metallic ions were connected with Pb/I inorganic clusters,and the organic cation acted as an electrostatic balance in the whole structure.Compounds from 7 to 10 are four supramolecular hybrid complexes with novel structures.Among them,compounds 7 and 8 formed a Cu/I one-dimensional chain-like structure of [Cu3I7]n4n-and [Cu8I12]n4n-,while compound 9 and 10 are zero-dimensional structures.The X-ray single crystal diffraction,X-ray powder diffraction,fluorescence spectroscopy,infrared spectroscopy,solid UV-visible conversion spectra,and thermogravimetric analysis were used in preliminary analysis and research of the complexes,providing basis for the further exploration of semiconductor materials and optoelectronic materials.