The Construction Of Metal Salts Based On CF₃ Containing Ethylenediamine Ligand And The Effect Of Functional Groups CF₃ On Mechanochemical Dehydrochlorination Reactions

Supramolecular chemistry mainly researches molecular recognition and self-assembly by non covalent bond interaction from molecule.Supramolecular usually consists of two or more chemicals,interacting to form the structure and function of supramolecular entities.In the original molecule other groups are introduced so that they have important influence on the original molecular optical,electrical,magnetic,reactivity properties,etc.basing on second sphere coordination and mechanochemistry.At present,the research has involved construction of receptors in organic chemistry,metal ion-ligand complexes synthesis in coordination chemistry,physical and chemical experiments and theory calculation,the process of life in life science and other fields.In this paper we firstly synthesized ligand of flexible chain N,N,N',N'-ptrifluoromethyl-tetrabenzyl-ethylenediamine?denoting L?,and we have obtained two polymorphs of ligand L?denoting ? and ??under different temperatures.The phase ?crystallizes in P2₁/n space group,Monoclinic system while phase ? crystallizes in P-1 space group,Triclinic system.Through the heating experiment,when the temperature up to 70?,phase ? has been completely transformed into phase ?.Then based on second-sphere coordination strategy,protonated ligand L interacts with metal chloride to form a quasi-chelating interaction motif [H₂L]²⁺[MCl₄]^2- in EtOH solution.The crystal 1 crystallizes in C2/c space group,Monoclinic system,while crystal 2 to 4 crystallizes in P2₁/c space group,Monoclinic system.Using crystal 1which forms a quasi-chelating interaction motif as structure unit,and then forms chain structure along b axis through the strong C-H...F interaction between structure units.Crystal 3,crystal 4 and crystal 2 are isostructure so they are adopted same interaction and space arrangement with crystal 2.their crystal cell parameters are very close to crystal 2 resulting in they all form chain structure along c axis.The above four kinds of hydrogen bonding salts in KOH or K₂CO₃ alkaline condition,by mechanical grinding,generating the raw material ligand.The grinding experiment finally couldn't transform into the corresponding complexes because of the influence of strong electron-withdraw group CF₃.This has also been conformed by DFT theory calculations.