Synthesis And Excited State Properties Of Soluble Metal Phthalocyanine Complexes

Today society is in information era of rapid development.The application of laser technology becomes more and more widely.The applications based on highlight optics develop rapidly.Accordingly,studies on nonlinear optical materials become more and more deeply.Phthalocyanines display outstanding NLO properties and become hotspot due to large π conjugated system.To obtain materials with large nonlinear optical properties,high solubility,and low face-to-face aggregation,a series of organic solvent soluble metallophthalocyanines and axially substituted indium phthalocyanines were synthesized,such as tetra-α-(3-pyridinyloxy)metallophthalocyanines[α-MPc(3-OPy)4,M:H2,Co,Ni,Cu,Zn,Pb;Py:pyridinyl],tetra-α-(2-ethoxyethoxy)metallophthalocyanines[α-MPc(OR)4,M:H2,Co,Ni,Cu,Zn,InCl;R:2-ethoxyethyl],axially substituted tetra-α-(2-ethoxyethoxy)indium phthalocyanines[α-In(R’)Pc(OR)4,R:2-ethoxyethyl;R’:ethyl(C2),n-propyl(C3),n-butyl(C4),n,pentyl(C5),n-hexyl(C6),n-octyl(C8),phenyl(Ph),p-methylphenyl(PhC),p-methoxyphenyl(PhOC),p-tert-butylphenyl(PhtBu),1-naphthyl(Naph)].The complexes were characterized by UV-Vis spectra,IR spectra,1H NMR,CHN elemental analysis,MALDI-TOF-MS,etc.Twenty-one novel metallophthalocyanine derivatives were never been reported.The third-order nonlinear optical(NLO)properties of α-MPc(3-OPy)4[M:Cu,Zn,Pb;R:pyridinyl]and α-MPc(OR)4[M:Ni,Cu,Zn,InCl;R:2-ethoxyethyl]were studied using Z-Scan technique with laser pulse width of 4 nanoseconds at the wavelength of 532 nm.The relationships between central metal,peripheral substituents and the third-order optical nonlinearities are studied.The results show that the second-order molecular hyperpolarizabilities γ get larger with increasing of atomic number of central atom.The γ value of zine phthalocyanine is sligthly smaller than that of copper phthalocyanine.The γ value of tetra-α-(2-ethoxyethoxy)metallophthalocyanines is large compared to tetra-a-(3-pyridinyloxy)metallophthalocyanines(M:Cu,Zn).Transient absorption spectrum and the lifetime of the first excited triplet state of a-MPc(OR)4[M:Zn,InCl;R:-OCH2CH2OCH2CH3)]and α-In(R,)Pc(OR)4 were determined using the technique of laser flash photolysis with laser pulse width of 4.5 nanoseconds at the wavelength of 410 nm.The results show that above phthalocyanines have T1-Tn absorption and the transient absorption spectra based on the first excited triplet state of above phthalocyanines are obtained.The lifetime of the first excited state of above phthalocyanines reaches microseconds,and the lifetime of axially substituted indium phthalocyanines is shorted than that of indium chloride phthalocyanine,except for a-In(PhOC)Pc(OR)4.