Design And Synthesis Of Rotor-stator Phase Transition Materials And Study On Its’ Properties

Rotor-stator materials have much attention due to their interesting molecular assembly and wide applications.It has emerged many functional rotor-stator materials with excellent properties of dielectric,phase transition,second-order nonlinear optical effects.Rotor-stator materials are mostly designed and synthesized based on18-crown-6.Crown ether molecules have a large cavity that can coordinate with organic amine cations using the interaction of hydrogen bonds,thus forming a rotor-stator model.In the process of discovering and exploring various superior materials,the initial challenge is how to rationally design materials,and then systematically construct rotor-stator materials.In the design of multifunctional crystals,it has been shown that the degree of cation-anion matching plays a crucial role in modulating second-order nonlinear effects.So how to transform this abstract momentum matching principle into concrete chemical means,and design high-quality functional rotor-stator type materials?The design idea of this paper is to use hydrogen bonds to construct complex rotor-stator materials,explore the effective model,and study the influence of halogen substituents on the crystal structure and properties.Thirteen chemical compounds were designed,synthesized,and characterized here.The research content of this paper can be divided into the following three parts:Part 1:Design,synthesis and research of organic cationic rotor-stator compound containing benzene ring.Seven rotor-stator compounds were synthesized using macromolecule 15-crown-5,benzyine derivatives（2,6-Difluorobrnzylamine,2-Chloro-6-Fluorobenzylamine,4-Bromobenzylamine,4-Fluorobenzylamine）,two tetraheic acids（HClO₄and HReO₄）.The seven compounds are,respectively,[（C₇H₈F₂N）（15-crown-5）][ClO₄]（1）,[（C₇H₈F₂N）（15-crown-5）][ReO₄]（2）,[（C₇H₈FClN）（15-crown-5）][ClO₄]（3）,[（C₇H₈FClN）（15-crown-5）][ReO₄]（4）,[（C₇H₉Br N）（15-crown-5）][ClO₄]（5）,[（C₇H₉Br N）（15-crown-5）][ReO₄]（6）,[（C₇H₉FN）（15-crown-5）][ReO₄]（7）.The structure,phase transition,dielectric,and second-order nonlinear optical properties are subsequently characterized.Part 2:Design,synthesis and research of organic cationic rotor-stator compounds containing quasi-spherical molecules.Three rotor-stator compounds were synthesized withmacromolecular15-crown-5,quasi-sphericalorganic cations（1,4-Diazabicyclo[2.2.2]Octane,1,5-Diazabicyclo[3.2.1]Octane）,three tetraheic acids（HClO₄,HBF₄,HReO₄）.The three compounds are[(C₆H₁₃N₂)（15-crown-5）₂][BF₄]₂·2H₂O（8）,[(C₆H₁₃N₂)（15-crown-5）₂][ReO₄]₂（9）,[(C₆H₁₃N₂)（15-crown-5）][ClO₄]（10）.The structure and the phase transition are characterized.Part 3:Design,synthesis and research of organic cationic rotor-stator compounds containing straight-chain molecules.Three rotor-stator compounds were synthesized using macromolecule 15-crown-5,straight-chain molecular organic cations（Ethylenediamine,N-Methylmonoethanolamine）,two tetraheic acids（HClO₄,HBF₄）.The three compounds are[(C₂H₁₀N₂)（15-crown-5）₂][ClO₄]₂（11）,[(C₂H₁₀N₂)（15-crown-5）₂][BF₄]₂（12）,[(C₃H₁₀ON)（15-crown-5）][ClO₄]（13）.The structure and the phase transition are characterized.The experimental results show that all the thirteen compounds have phase transition except for compound 12.Among them,compounds 1～7 have a dielectric response,compounds 2,3,4 have a reversible SHG signal response.The design strategy of this paper effectively explores a variety of good performance phase transition materials.Three chemical design methods,including the use of halogen substitution,introduction of quasi-spherical molecules and introduction of straight amine,provide valuable guidance for the targeted design of functional rotor-stator type materials.