| Metal-organic fluorescent responsive materials,which exhibit advantages both of the stability of inorganic materials and the designability of organic materials,show potential application on sensors,anti-counterfeiting,information storage,biological probes and so on.Among which,monovalent copper coordination complexes have attracted widespread attention due to their advantages of low price,abundant resources,environmentally friendly,diverse structures,rich optical properties and so on.In this thesis,a series of coordination complexes with rich structural types have been designed and synthesized by assembly of nitrogen-containing and phosphine-containing ligands with monovalent copper.The crystal structures of the complexes have been determined by X-ray single crystal diffraction.The complexes have been characterized by X-ray powder diffraction,infrared spectroscopy,ultraviolet spectroscopy,elemental analyses,thermogravimetric analyses,and fluorescencent spectroscopy.With the aid of theoretical calculation,the structure-property relationship has been studied.In addition,the multiple stimuli fluorescence responsive properties of different types of complexes have been studied.Meanwhile,the fluorescence responsive mechanism has been analyzed.The main research contents of the thesis are listed as follows:1.Assemblies and vapor-induced fluorescence responses of monovalent copper molecular complexes.Seven monovalent copper molecular complexes have been designably synthesized with monovalent copper as the center and both of nitrogen and phosphine containing ligands,namely:(1)Cu2(?-I)2[Py]2[TPP(p-OCH3)]2,(2)Cu2(?-I)2[Py(p-CH3)]2[TPP(p-OCH3)]2,(3)Cu2(?-I)2[Pyz(o-CH3)]2[TPP(p-OCH3)]2,(4)Cu2(?-I)2[Py(m-NH2)]2[TPP]2,(5)Cu2(?-I)2[Py(p-N H2)]2[TPP]2,(6)Cu2(?-I)2[DPPB]2,(7)Cu4(?3-I)4[Py(m-Ph)]4.Complexes 1-6 show binuclear structures with Cu2(?-I)2 as the center,while complex 7 exhibits a tetranuclear structure with Cu4(?3-I)4 as the center.With the aid of theoretical calculation,it was speculated that the nitrogen-containing ligand mainly affected the energy level of the LUMO orbital,and changed the energy level difference between the HOMO and LUMO orbital,so as to adjust the emission wavelength.The emission of complexes 1-3 and 5 may mainly derive from metal to ligand charge transfer(MLCT)as well as halogen to ligand charge transfer(XLCT).The fluorescence responses of crystals,films,PMMA doped films and test paper of complexes Cu2(?-I)2[Py(p-C2H3)]2[TPP(p-OCH3)]2 and 1 to nitrogen-containing heterocyclic organic vapor have been studied.The films,PMMA doped films and test paper showed high sensitivity.It was speculated that the fluorescence responsive mechanism may be attributed that nitrogen-containing heterocyclic vapor replaced the nitrogen-containing ligand in the complex,which changed the energy level of the LUMO orbital,so as to realize the fluorescence response.It was found that Cu2(?-I)2[Py(p-C2H3)]2[TPP(p-OCH3)]2 test paper showed sensitive fluorescence response to cigarette smoke.It was assumed that the mechanism may be assigned that the nitrogen-containing ligand in the complex was replaced by nicotine in the smoke so as to realize the fluorescence response.The designedly synthesized test paper of complex 5 exhibited good fluorescence response to formaldehyde vapor.It was speculated that the mechanism may be due to the in-situ Schiff base reaction occurred between the amino group of nitrogen-containing ligand in complex 5 and formaldehyde,which led to the fluorescence response.2.Assemblies and multiple stimuli fluorescence responses of monovalent copper ionic complexes.Two ionic complexes have been assembled by tris(2-methylphenyl)phosphine and bis(diphenylphosphine)methane as phosphine ligands and monovalent copper respectively,namely:(8){Cu[TPP(o-CH3)][CH3CN]3}+{Cu2(?-I)3[TPP(o-CH3)]2}-,(9){Cu3(?3-I)2[DPPM]3+{I3}-·CH3CN.In complex 8,the cation shows a mononuclear copper structure,while the anion exhibits a dinuclear copper structure with Cu2(?-I)3 as the center.In complex 9,the cation shows a trinuclear copper structure with Cu3(?3-I)2 as the center,while the anion is I3-,with the acetonitrile solvent molecule filling in.The crystals of complex 8 showed good fluorescence response to mechanical force.The crystals and test paper of 8 exhibited good fluorescence response to organic nitrogen-containing heterocyclic vapor.While the crystals of 8 showed good fluorescence response to methylbenzene vapor.Meanwhile,the solution of 8 exhibited good fluorescence response to Fe3+.The responsive mechanism may be attributed that grinding led to the leave of acetonitrile to make the reconstruction of the structure,the nitrogen-containing heterocyclic vapor complementally coordinated to Cu,methylbenzene filled in the structure as solvent molecule,Fe3+replaced the coordination.Thus,the structure of complex 8 changed to realize the fluorescence responses.3.Assemblies and mechanically-induced fluorescence responses of monovalent copper coordination polymers.Three one-dimensional chain-like coordination polymers have been synthesized by using pyridine derivatives as nitrogen-containing ligands,1,3-bis(diphenylphosphine)propane or triphenylphosphine as phosphine ligands and monovalent copper respectively,namely:(10){Cu I[Py(p-CH3)]}n,(11)Cu2(?-I)2[Py]2[DPPP]2}n,(12){Cu2(?-I)2[Py(p-CH2NH2)]2[TPP]2}n.Complex 10 shows a mononuclear one-dimensional chain structure,while 11 and 12 exhibit binuclear one-dimensional chain structure with Cu2(?-I)2 as the center.All of complexes 10-12 showed excellent mechanically-induced fluorescence responsive properties.It was speculated that the mechanism may be attributed that grinding led to the change of Cu···Cu distance,which made the cluster core charge transfer(3CC)playing a leading role,so as to realize the fluorescence response. |
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