Synthesis And Nonlinear Optical Properties Of Metal-Phthalocyanine Derivatives

The thesis is divided into two parts.The first part focuses on the synthesis and characterization of metal-phthalocyanines and their derivatives. The second part reports the estimation of organic second-order nonlinear optical coefficient of the metal-phthalocyanine derivatives. In the first part,we synthesized four metal-phthalocyanines.They are oxotitanium phthalocyanine (TiOPc),copper phthalocyanine (CuPc),magnesium phthalocyanine (MgPc) and aluminium phthalocyanine.Among them, TiOPc was synthesized in solvent and its productivity was 80.3%.The others were synthesized in solid and their productivities were52.7%,47.1% and 38.5%.IR and element analysis characterized the structures of products.The result shows that the IR data reflects the characteristic absorption spectrum of phthalocyanines and resembles with standard spectrum.In addition,the mechanism of synthesizing metal-phthalocyanine was studied deeply. Metal-phthalocyanines reacting with chlorosulfonic acid (HSO₃Cl) resulted new compounds chlorosulfonic-acid-metal phthalocyanines . Those compounds contain SO₂Cl-group which enhances metal phthalocyanines, reactivity and dissolubility.The reacting result show that only CuPc and TiOPc had reacted with HSO3Cl. MgPc and AlPc didn't react because of the action of strong acid on metal.When a little sodium hydroxide was added in the reaction container,white deposit appeared,which means that metal phthalocyanines(MgPc and AlPc)were decomposed and they produced Mg2+and Al3+ ions . Reaction condition affected the yields of chlorosulfonic-acid-metal phthalocyanines.IR and element analysis characterized the structures of products of CuPc-SO₂Cl and TiOPc-SO₂Cl. The result of element analysis showed one-molecule chlorosulfonic-acid-metal phthalocyanines contained about one-molecule SO₂Cl-group. Carbazole sulfonates metal phthalocyanines were synthesized by reaction between CuPc--SO2C,TiOPc--SO2Cl and carbazole.IR and element analysis characterized the structures of products of carbazole sulfonates metal phthalocyanines.The optimum conditions of synthesizing carbazole sulfonates TiOPc were n (TiOPC-SO2Cl) : n (carbazole)=1 : 1.5,reaction temperature 150℃and reaction time 240min.The yield of compound was 75.2%. Those compounds have two organic groups (Carbazole-group and metal phthalocyanine-group) which bond with two sides of —SO2—group forming a ∧shape organic structure. In the second part,the values of the nonlinear optical second-order polarizabilities and the ground state permanent dipole moments(βCTμg) were calculated by a non-laser evaluation method —the solvatochromic method.the values of βCTμg of carbazole sulfonates TiOPc and carbazole sulfonates CuPc compounds were about 3.39 ×10-29esu.D and 3.71×10-29 esu.D.This means that Carbazole sulfonates metal phthalocyanine compounds are latent second order optical materials.