Synthesis,Crystal Structure And Properties Of Functional Coordination Compounds Based On Transition Metal Precursors

Functional coordination compounds have potential applications in the fields of chemistry and materials due to their diverse structure and excellent optical,electrical,magnetic and catalytic properties.In recent years,the design,synthesis and properties of functional coordination compounds have attracted much attention for coordination chemistry research.More and more synthetic methods and strategies of functional coordination compounds have been reported,in which the most effective synthetic method of functional coordination compounds is the self-assembly by using secondary building units（SUBs）as precursors and introducing new groups.In this paper,based on five kinds of secondary building units as precursors,seven kinds of functional coordination compounds with unique structures have been designed and prepared by coordination with two nitrogen-heterocyclic ligands and two second metal central ions,respectively.Their structures and thermal stability properties have been studied by infrared,elemental analysis,X-ray single-crystal diffraction and thermogravimetric analysis.In addition,some of them have been characterized by Z-scan and exhibit good nonlinear optical absorption properties,while the magnetic properties of rest have also beeen studied.In the chapter 2,using two kinds of dimers of metal ruthenium[Ir（MPPy）₂Cl]₂and[Ir（PPya）₂Cl]₂ as precursors,metallic pyridazine complexes 1–4 have been synthesized by introducing them into three pyridazine ligands DpTz-Ph,DpTz-PhA and DpTz-MPh,respectively.Their crystals are obtained by inter-diffusion method.1and 2 belong to the triclinic and monoclinic systems,respectively.3 and 4 both crystallize in the orthorhombic system.The Z-scan studies indicate that they all have good nonlinear optical absorption properties.[Ir（MPPy）₂]（PyTz-Ph）（PF₆）·DCM（1）[Ir（MPPy）₂]（PyTz-PhA）（PF₆）·DCM（2）[Ir（PPya）₂]（PyTz-MPh）（PF₆）（3）[Ir（PPya）₂]（PyTz-Ph）（PF₆）（4）A porphyrin ligand TMbPyP is synthesized by designing a single pyridine active site at the periphery of porphyrin.Then,the precursor[Ir（DfPPy）₂Cl]₂ is introduced into the active site of the ligand TMbPyP to prepare metallic porphyrin complex 5,and its crystal is obtained by the secondary growth method.5 crystallizes in the triclinic system.The Z-scan data indicates that 5 reveals better nonlinear optical absorption property than ligand TMbPyP.This behavior is mainly attributed to the fixed-point introduction of precursor[Ir（DfPPy）₂Cl]₂,which change the structure of porphyrin ligand TMbPyP,and realize the regulation of its nonlinear optical property.[Ir（DfPPy）₂Cl]（TMbPyP）（5）Chapter 4 designs and synthesizes two metallic precursors L^Cu and L^Co,according to the nitrogen-containing ligand 2,4-dicarboxylic acid pyridine connected with the transition metal central ions Cu^Ⅱ and Co^Ⅱ,respectively.Two novel heterobimetallic coordination compounds（HCCs）6 and 7 with porous 3D structure are prepared by self-assembly of L^Cu/Er^Ⅲ and L^Co/Ca^Ⅱ,using the inter-diffusion method and the solvothermal synthetic method,respectively.The crystals of 6 and 7severally belong to the triclinic and monoclinic systems.Magnetic measurements illustrate that both 6 and 7 exhibit antiferromagnetic properties,which may be attributed to the crystal field splitting of the spin metal center ions and their orbital coupling.{[Er₂（DMSO）₄][L^Cu]₃·2DMSO·6CH₃OH}_n（6）{[Ca（H₂O）₂][L^Co]·DMSO·2H₂O}_n（7）...