Planar Binuclear Phthalocyanine-Containing Sandwich- Type Rare-Earth Complexes: Synthesis, Spectroscopy, Electrochemistry, and NLO Properties

摘要

The mixed cyclic tetramerization of 4,5-bis(hexylthio)- phthalonitrile and bis(diiminoisoindoline) with [M(acac)_3]· nH_2O (M = Pr, Eu, Lu) as template in the presence of 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol at reflux has provided binuclear phthalocyanine-containing sandwich- type rare-earth complexes [{Pc(SC_6H_(13))_8}M{BiPc- (SC_6H_(13))_(12)}M(SC_6H_(13))_8] (M = Pr, Eu, Lu; 1-3). These new binuclear phthalocyanine-containing sandwich compounds have been characterized by a series of spectroscopic methods including mass spectrometry and 1H NMR, electronic absorp- tion, and IR spectroscopy in addition to elemental analysis. Their electrochemical data have also been obtained by cyclic voltammetry. In addition, the third-order nonlinear optical properties of [{Pc(SC_6H_(13))_8}Pr{BiPc(SC_6H_(13))_(12)}Pr(SC_6H_(13))_8] (1) and [Pr{Pc(SC_6H_(13))_8}_2] in toluene solution were studied comparatively by using the Z-scan technique; effective imaginary third-order molecular hyperpolarizabilities of 1.86×10~(- 11) and 1.56×10~(-11) esu, respectively, were obtained, which indicates their potential application in the optical-limiting field.