Ferrocenyl Modified The Sandwich-type Porphyrin, Phthalocyanine Complexes Synthesis, Characterization, And Electrochemical Studies

Since the sandwich-type(phthalocyaninato)(porphyrinato) rare earth complex was synthesized,all kinds of sandwich-type rare earth complexes were synthesized and researched deeply.In all these complexes,two or three macrocyclic chromophores are held in close proximity,as become the base of abundant properties of this family of complex.This family of complex show extraordinary optic, electronic and magnetic properties.The huge potential as materials of novel molecular conductor,molecular semi-conductor,molecular magnet,gas-sensor, electrochemically generated multicolor response and electronic field directed luminescence etc.Our research work in this field has been focused on the following respect:1.Electrochemistry of Heteroleptic(phthalocyaninato)(porphyrinato) rare earth double-decker ComplexesA series of four(phthalocyaninato)(porphyrinato) rare earth double-decker complexes M(Pc)[Por(Fc)₂][Pc=phthalocyaninate;[Por(Fc)₂= 5,15-di(ferrocenyl)-porphyrin;M=Eu,Y,Ho,Lu](1-4) with two ferrocenyl units at the meso-positions of porphyrin ring have been designed and prepared.Electrochemical studies of these novel sandwich double-decker complexes revealed two consecutive ferrocene-based one-electron oxidation waves,indicating effective electronic coupling between the two ferrocenyl units attached at porphyrin meso-positions induced via sandwich structure of tetrapyrrole rare earth complexes.Nevertheless,the separation between the two consecutive ferrocene-based oxidation waves increases along with the decrease of rare earth ionic radius,indicating the effect of rare earth size on tuning the coupling between the two ferrocene centers linked with sandwich bis(tetarpyrrole) rare earth framework.For the purpose of comparative studies, (phthalocyaninato)(porphyrinato) europium triple-decker counterpart Eu₂(Pc)₂[Por(Fc)₂] (5) was also synthesized and electrochemically studied,confirming the tunable electronic interaction between the porphyrin meso-attached two ferrocene centers through changing the linking sandwich framework from double-decker to triple-decker.2.The molecular structures of 4,5-Diaminobenzene-1,2-dicarbonitrileWe have prepared 4,5-Diaminobenzene-1,2-dicarbonitrile and determined the molecular structures.In the crystal,the molecules are linked by four different N…H—N intermolecular hydrogen bonds between primary amido hydrogen atoms and amido and cyano nitrogen atoms.