Synthesis And Properties Of Sandwich-type Porphyrin, Phthalocyanine, Helicenocyanines Metal Complexes

Large conjugated π electron systems are pulled to a short distance by rare earthmetal ions in the sandwich-type rare earth complexes of porphyrin-phthalocyaninemolecule, showing the unique optical, electrical and magnetic properties. So thecomplexes have great application prospects used as molecular electronic conductors,molecular magnets and nonlinear optical materials and they have been the focus forresearchers in recent decades.First of all, nine mixed rare earth triple-deckers M2[TO(OH)PP](Pc)2[M=La…Dy,except Pm, Y and Ho…Lu; H2Por=5-(4-hydroxy)-10,15,20-tris(4-octyloxy)porphyrin, Pc=unsubstituted phthalocyanine] with tervalent rare earths wereprepared, and the infrared (IR) data of them have been collected. ForM2[TO(OH)PP](Pc)2], the IR spectra reveal that the frequencies of pyrrole stretching,isoindole breathing, and aza stretchings are decreased sensitive to the rare earth ionicsize, and remain basically unchanged along with the lanthanide contraction. Besides,the cerium metal ion in the IR spectrum of Ce2[TO(OH)PP](Pc)2] exists asintermediate valence state between III and IV. Compared with the double-deckers, theπ-π interactions in these mixed triple-deckers are weaker.Secondly, the Raman spectroscopic data in the range500-1800cm-1for a series of15rare earth double-deckers with tervalent rare earths M[Pc(MeOPhO)8]2(M=Y,La…Lu, except Ce, Pr and Pm), reduced state HPr[Pc(MeOPhO)8]2andintermediate-valent cerium Ce[Pc(MeOPhO)8]2have been collected using laserexcitation source emitting at632.8nm. The typical Raman marker bands of themonoanion radical [Pc(MeOPhO)8] were observed at1500-1528cm-1as very strongbands resulting from the coupling of pyrrole C=C and aza C=N stretchings. ForCe[Pc(MeOPhO)8]2and HPr[Pc(MeOPhO)8]2, a very strong band at1499cm-1wasthe marker Raman band of [Pc(MeOPhO)8]2. In addition, the influence of ionicradius of the rare earth metal and substituent species on the Raman scattingcharacteristics of sandwich-type compounds has also been tentatively studied.Finally, the precursor ligands of Hc were prepared, and were tried to makesandwich-type rare earth complexes using rare earth metal salts.