Design, Preparation And Properties Study Of Tetrapyrrole Metal Complexes

Porphyrins and phthalocyanines have unique 18?electrons conjugated planar structure and cavity structures that coordinate multiple metal ions.And they can form complexes of the planar structure with the transition elements and sandwich-type complexes with rare earth metals.Porphyrins,phthalocyanines and its derivatives have superior physical and chemical properties and excellent photoelectric properties.Thus they have potential application value in the fields of nonlinear optical materials,liquid crystal materials,electrochromic materials and field effect transistors.The first part of this paper,based on the synthesis of three kinds of complexes M^III?Pc?₂,M^III?OOPc?₂ and M^III[Pc?SPh?₈]₂?M=Y,Ce......Lu,except for La and Tm?,a detailed study was conducted on the IR and UV-vis of symmetric double-decker sandwich rare earth phthalocyanine complexes.For M^III[Pc?SPh?₈]₂,the electronic absorption spectra showed that the Soret and Q bands are blue-shifted,and especially the Q bands at 705–726 nm clearly become stronger along with the decrease of rare earth ion radius.The infrared characteristic absorption peaks for the phthalocyanine anion radical[Pc?SPh?₈]^·-were observed at 1311-1323 cm^-1 as the strongest absorption bands,which can be ascribed to the pyrrole stretching.In addition,the typical IR absorption bands of phthalocyanine radical anion[Pc?SPh?₈]^·-move to the high energy as the decrease of rare earth metal ionic radius.These facts suggest that the?-?electron interaction in these double-deckers becomes stronger along with the lanthanide contraction.In the second part,?-position and?-position octasubstituted free phthalocyanines,H₂Pc(?-OC₈H₁₇)₈ and H₂Pc??-OMe?₈ have been synthesized.The transition elements were introduced into the phthalocyanine ring to synthesize M^II[Pc??-OMe?₈]?M=Fe,Co,Cu,Mn?.These compounds have been simply characterized by MS,¹H NMR,IR and UV-vis characterization methods.The effect of the position,type,numbers of substituents and metal ions on the electron absorption spectrum of phthalocyanine have been detailed studied.In the third part,three kinds of porphyrins H₂?TOP?Por,H₂?TPP?Por and H₂[TP?OH?]Por were prepared.Then monolayer porphyrin rare-earth complex was used as template to undergo a tetramerization reaction with the phthalocyanine precursor to synthesize a hybrid porphyrin phthalocyanine complex M^III?Pc??Por*?.The complexes M^III?Pc?[TP?OH?Por]and M^III?Pc?[TP?OH?Por]were conducted a preliminary study.