Syntheses,Structures And Properties Of Supramolecular Crystals With Nitrogenous Ligands

Self-assembly supramolecular crystals have desired structures and expected functions,which is an important researching direction for the functional crystal materials.Due to a variety of combinational ways of nitrogenous ligands,thousands of supramolecular crystal structures appeared.However,some specific nitrogenous ligands form the certain trend for crystallization,followed by the specific functions.This is the formal mode for crystallization technique:select a specific ligand-form successional crystals-test performance comparison.In this paper,we synthesized a series of nitrogenous ligands and reported 6 different types of supramolecular crystals through evaporation,diffusion,settling,solvothermal,hydrothermal methods.Finally,the changing structures induce the changing fluorescent properties.Chapter one is introduction.According to the goal,fluorescent crystal and adsorption crystal materials are introduced respectively.For the fluorescent material,the concept of fluorescent organic small molecular crystal is derived from the concepts of supramolecular crystals and organic light emitting materials,and some related works are presented.To contrast the similarities and differences,the traditional luminous metal-complex showed.For the adsorption materials,some stable supramolecular crystals are elaborated about gas,anion/cation,solvent adsorption.Chapter two is experimental part.The synthesis of series ligands of[L1]-[L6]are introduced,the same to reagents,instruments and characterization;the synthesis of crystals[1]-[6]are introduced,the same to infrared,elemental analysis data.Chapter three is results and discussion.Six different types of supramolecular crystals formed by ligand 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)benzene[L1],1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)benzene[L2],?-Amino-?-(pyrid-2-yl)-acrylonitrile[L6]:Cu2(L6)[1],Ag(L6)(NO3)[2],[Cu(L1)0.5(CN)]·(H2O)4·(DMSO)3[3],[L2](DMA)2[4],[L2]n[5],[L2](HCl)4(H2O)6[6],exploring and comparing the difference fluorescent properties based on the structures of supramolecular crystals.(1)For the supramolecular crystals 1-2 of L6:Ag(I)plays a stimulative role for fluorescence.(2)For the supramolecular crystals 3-6 of L1-L2:the non-conjugated ligand L1 has a luminescence quenching effect contrasting with 3 and 4-6;the coordination solvent DMA plays a hinder role contrasting with 4 and 4'(the crystal phase of solvent of 4 losing);the twisted ligand L2 plays a stimulative role contrasting with 4' and 5;the coordination solvent HCl has a luminescence quenching effect contrasting with 4-5 and 6.Subsequently,the performance objectives,synthesis schemes and attempts for the crystals forming about ligands 1,3,5-tri-(4-(3,5-dicyano-2,6-dipyridyl)trihydropyridyl)benzene[L3],1,2,4,5-quadri-(4-(3,5-dicyano-2,6-dipyridyl)quadrihydropyridyl)benzene[L4]are introduced.Large aperture MOFs materials are formed through ligand 2,4-dicyano-1,3,5-tripyridylpyridine[L5].In the final of this paper,a summary and an outlook are represented.