Structure,Phase Transition And Optical Properties Of Hybrid Metal Halides Dominated By Halogen Bonds

Hybrid Organic-Inorganic Metal Halides are a kind of hybrid complexes formed by the self-assembly of organic cations and inorganic halogen metal acid anions.Its structure is diverse,the performance is unique,in many fields such as photovoltaic,magnetic,ferroelectric and so on has the extensive application.Among them,the hybrid manganese halide and lead halide complexes have attracted the attention of researchers because of their superior optical properties.Traditional hybrid metal halides usually combine organic ammonium primary or secondary ammonium cations with inorganic anions,and the hydrogen bond between the cation and the anion can increase the stability of the complex.However,the presence of hydrogen bonds also causes the material to be unstable to moisture.Halogen bond as a kind of similar to hydrogen bonding strength and highly directional non covalent force,also can be potentially used in the construction of a hybrid metal halide material,and the significant hydrophobicity can be used to supplement a powerful hydrogen bonding material,so the halogen key dominant hybrid metal halide in the traditional hybrid material is superior performance on the basis of given higher stability and a greater degree of structure and performance of regulatory.Based on the above analysis,a series of hybrid halogen-manganic acid and halogen-lead-acid complex crystals containing halogen bonds were synthesized in this paper.The effects of halogen bonds on the structure and luminescence properties of hybrid halides were studied as follows:(1)In the first chapter,the sources and applications of organic-inorganic hybrid metal halides are briefly introduced,then three common methods for preparing hybrid metal halides are proposed,and the structure types of organic-inorganic hybrid metal halides 3D-0D are summarized.The hybrid materials of manganese halide and lead halide are analyzed and their shortcomings are pointed out.In addition,as a halogen key and hydrogen bonding similar non covalent force,since it has a more flexible regulatory,polarizability and significant hydrophobic powerful supplement can be used as a hydrogen bond,based on the bittern key excellent characteristics,the present paper selected topic significance and research purposes,through the introduction in organic-inorganic hybrid metal halide halide keys to control the structure and optical properties,to get rich structure,superior performance of organic-inorganic hybrid metal halide material.(2)the paper second chapter through the system to change the halogen type supplied in organic and inorganic components,synthesis of a series of dominated by halide key zero dimensional hybrid halide manganese compound crystal(X1PhTMN-MnX2)(X1=Cl,Br,I,X2=Cl,Br)(1-6),are analyzed in detail by using X-ray diffraction crystal structure of this series of compounds,the transient fluorescence technology is studied by steady state-their photoluminescence behavior,and explore the halide button-hybrid composite structures-the connection between the luminescence performance.In addition,a hybrid bimetallic halide BrPhTMN-MnxCo1-xBr(8)containing both manganese and cobalt was prepared based on a hybrid cobalt halide complex BrPhTMN-CoBr(7)with similar structure but different luminescence behavior as 2,which further adjusted the luminescence properties of the hybrid materials.Compound 4 has a new hybrid structure 9 by thermal transformation at high temperature.The comparison of the series of structures shows that the halogen bond plays a leading role in the transition behavior.(3)In the third chapter,the hybrid iodio-lead acid hybrid ITMN-PbI(10)and the mixed halogen hybrid ITMN-PbIBr(11)and ITMN-PbICl(12)were synthesized by using the strong organic halogen donor ITMN-I and lead halide.The hybrid chloro-lead-acid complex ITMN-PbCl(13)was obtained by the reaction of ITMN·Cl with PbCl2.Similarly,these structures were analyzed and systematically compared by X-ray diffraction,and their photoluminescence properties were characterized by steady-transient fluorescence,and the relationship between halogen bond,complex structure and luminescence behavior was discussed.Complex 10 is transformed into complex 14 under the irradiation of xenon lamp,and the photochromic phenomenon is followed.The intrinsic reason of the photochromic phenomenon is explained by structural analysis in this paper.(4)In the last chapter,the relationship between the halogen-complex structure and luminescence behavior in hybrid manganese halide and lead halide complex is summarized,and the idea of rationally regulating the halogen-bond to improve the stability of hybrid complex and obtain organic-inorganic hybrid metal halide materials with superior performance is put forward.