Synthesis And Characterizations Of Porphyrin, Naphthalocyanine Rare Earth Metal Complexes

Porphyrins and phthalocyanines (naphthalocynines) are highly conjugatedmacrocyclic ligands, which are very easy to form sandwich complexes with rare earthmetals. The sandwich rare earth metal complexes have unique optical, electrical,magnetic and other physical properties because of the intriguing inter-ring π-πinteractions, in addition, they have attracted much attention and are currently underintensive study as potential materials for molecular conductor, gas sensing, non-linearoptics, optoelectronic conversion, molecular electronic devices and so on.First of all, a new series of eleven sandwich rare earth complexesM[2,3-Nc(SPh)8]2(M=Y, Ce···Er, except for Pm) have been synthesized and theUV-vis absorption and IR spectrum have been described systematicly. The UV-visabsorption and IR absorption spectrum show the metal ions in the compoundsM[2,3-Nc(SPh)8]2(M=Y, Ce···Er, except for Pm) exist in the form of trivalent. Inaddition, the Q-band of UV-vis absorption and the typical characteristic absorptionpeak of naphthalocyanine radical anion [Nc(SPh)8]· in IR spectroscopy (located in1319-1325cm-1) move to the higher wavenumber as the the metal ionic radius reduce,which show that as the decreases of the size of the metal ion, the π-π electroninteractions between the rings become stronger.Secondly, this paper synthetizes a new series of eight mixed sandwich rare earthcomplexes M(TNOPP)[Nc(SPh)8](M=La···Dy, except for Ce and Pm) and providesthe UV-vis absorption spectra data, IR spectra data and raman spectra data, moreover,1H NMR is detected to confirms their structure further. It should be pointed out thatthe typical characteristic absorption peak of naphthalocyanine radical anion[Nc(SPh)8]· exists both in the IR and Raman spectra of complexesM(TNOPP)[Nc(SPh)8](M=La···Dy, except for Ce and Pm), which located in1316-1323cm-1and1512-1524cm-1respectively and the two peaks blue-shifted asthe decreases with the size of the metal ion decreasing. It can be concluded that theπ-π electron interactions between the rings become stronger as the the metal ionicradius reducing, which is consistent with the conclusions of electronic absorptionspectra.