Synthesis,Characterization And Fluorescence Properties Of Olefin-Cu(?) Coordination Compounds

Stable olefin-copper?I?complexes have many interesting physical properties such as fluorescence,ferroelectric,dielectric,chiral resolution and electrochemical properties.The preparation of olefin-copper?I?complex requires an oxygen-free environment and which is difficult to synthesis.A series of olefin ligands were synthesized base on the heterocyclic organic compounds such as 2,5-dimethylpiperazine,1,4-bis?2H-tetrazol-5-yl?benzene and1-vinylimidazole by reviewing a large number of papers.The pressure-resistant Pyrex glass tube was used,and the air in the tube was evacuated by a vacuum pump to obtain a vacuum environment.Under solvothermal conditions,the ligands were reacted with CuX?X=Cl,Br,I?to obtain six olefin-copper?I?complexes and three nitrogen-containing heterocyclic complexes.The crystal structures were determined by single crystal X-ray diffraction,and its fluorescent,dielectric were investgated.1.1,4-diallyl-2,5-dimethylpiperazine ligand?DADMP?as the building block,which was react with CuCl and CuBr respectively to obtain three olefin-copper?I?complexes:[Cu₃Cl₄?DADMP?]_n?1?;[Cu₃Br₄?DADMP?₂]_n?2?;[Cu₂Br₂?DADMP?]_n?3?;Their crystal structures were characterized by the X-ray single crystal diffractometer.The coordination environment of complex 1 showed that the 2,5-dimethylpiperazine ring was present chair conformation in the molecular structure of ligand DADMP.And the C=C double on both sides were coordinated with copper?I?ion,the N atom on the piperazine ring can't coordinated with the copper?I?ion,and the Cu?I?ion has three different coordination modes.The ligand connected with one-dimensional copper cluster chains to form two-dimensional planar structure.In complex 2,the DADMP ligand molecule have two different coordination modes,the double bond and two N atoms from the ligand are coordinated with copper?I?ion;The double bond are from the other molecule of the ligand are coordinated with the copper?I?,the N atom in the ligand was protonated so does not participate in the coordination.One-dimensional copper chains are connected with two different coordination modes of DADMP ligands to form two-dimensional planar structure.In the complex 3,the double bond and the N atom in the ligand are coordinated with the copper?I?ion to form a two-dimensional layered structure.Dielectric tests show that the dielectric constants of complexes 1 and 3 increasing by temperature.Fluorescence tests showed that complexes 1 and 3 produced yellow fluorescence and green fluorescence,respectively.2.1-?4-vinylbenzyl?-2,5-dimethylpiperazine ligand?DMVBP?as the building block,reacting with CuCl and CuBr respectively to obtain two olefin-copper?I?complexes:[Cu₂Cl₃?DMVBP?]_n?4?;[Cu₂Br₃?DMVBP?]_n?5?;Their crystal structures were characterized by an X-ray single crystal diffractometer.The coordination environment of complex 4 showed that the 2,5-dimethylpiperazine ring was appear a chair conformation in the molecular structure of DMVBP,unilateral4-vinylbenzyl C=C double bond and the N atoms in the liand are all coordinated with the copper?I?ion.There are two coordination modes in the complex 5,and the ligands are connected with the copper clusters to form one-dimensional chain structure.The coordination environment of complexes 4 and 5 is similar.In the complex 5,and the ligands are connected with copper clusters to form a one-dimensional chain structure.Fluorescence tests showed that complexes 4 and 5 both are emitted green fluorescence.3.1,4-bis?2-allyl-2H-tetrazol-5-yl?benzene ligand?BATB?as a building block,reacting with CuBr to obtain a three-dimensional olefin-copper?I?complex:[CuBr?BATB?]_n?6?;Their crystal structures were characterized by an X-ray single crystal diffractometer.The coordination environment of complex 6 showed that the allyl C=C double bond and the N atom on the ligand BATB were coordinated with the copper?I?ion.There are three coordination modes of the complex 6,and the Br atom acts as a bridge bound to connect with the copper?I?ion to form a two-dimensional planar structure.The ligands were connected by copper clusters to form a three-dimensional network structure.Fluorescence tests showed that the complex 6 emitted orange-red fluorescence.4.1-vinylimidazole?VMZ?ligand as building block reacting with CuX?X=Cl,Br,I?to obtain three nitrogen-containing heterocyclic complexes:[Cu₄Cl₆O?VMZ?₄]?7?;[Cu_5.5Br₇?VMZ?₇]_n?8?;[Cu₄I₄?VMZ?₄]?9?;Their crystal structures were characterized by the X-ray single crystal diffractometer.The coordination environment of the complex 7 shows that the N atoms are from1-vinylimidazole ring was coordinated with the copper ion,and which has a coordination mode.The coordination environments of complex 8 shows that the N atoms come from the ligand are coordinated with monovalent and divalent copper?I?ions,respectively and there are six coordination modes,which showing a central symmetrical structure.The coordination environment of the complex 9 shows that the N atom come from the ligand are coordinated with copper?I?ions and there was a coordination mode.The C=C in organic ligand coordinate without copper?I?ion.Fluorescence tests show that complexes 7,8 and 9emit purple,blue and red fluorescence,respectively,which can be used as potential luminescent materials.