A series of metal complexes of tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine, [Py8TPyzPzH2], having the general formula [Py8TPyzPzM]âxH2O (M ) MgII(H2O), MnII, CoII, CuII, ZnII; x ) 3-8) were synthesized by reaction of the free-base macrocycle with the appropriate metal acetate in pyridine or dimethyl sulfoxide under mild conditions. Clathrated water and retained pyridine molecules for the MnII and CoII species are easily eliminated by heating under vacuum, the water molecules being recovered by exposure of the unsolvated macrocycles to air. Magnetic susceptibility measurements and EPR spectra of the materials in the solid state provide basic information on the spin state of the CuII, CoII, and MnII species. Colloidal solutions caused by molecular aggregation are formed in nondonor solvents (CH2Cl2, CHCl3), a moderately basic solvent (pyridine), and an acidic solvent (CH3COOH), with the extent of aggregation depending on the specific solvent and the central metal ion. UV-vis spectral monitoring of the solutions after preparation indicates that disaggregation systematically occurs as a function of time leading ultimately to the formation of clear solutions containing the monomeric form of the porphyrazine. Cyclic voltammetry and thin-layer spectroelectrochemistry show that each compound with an electroinactive metal ion undergoes four reversible one-electron reductions, leading to formation of the negatively charged species [Py8TPyzPzM]n- (n ) 1 - 4). The stepwise uptake of four electrons is consistent with a ring-centered reduction, but in the case of the cobalt complex a metal-centered (CoII f CoI) reduction occurs in the first process and only three additional reductions are observed. No oxidations are observed in pyridine or CH2Cl2 containing 0.1 M tetrabuthylammonium perchlorate (TBAP). The nonlinear optical properties (NLO) of the species [Py8TPyzPzM] (M ) 2HI, CuII, ZnII, MgII(H2O)) have also been examined with nanosecond pulses at 532 nm in dimethyl sulfoxide solution. Reverse saturable absorption is shown by all of the [Py8TPyzPzM] species, which exhibit distinct behavior depending on the nature of M and extent of aggregation.
Tetra-2,3-pyrazinoporphyrazines with externally appended pyridine rings. 2. Metal complexes of tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine: Linear and nonlinear optical properties and electrochemical behavior
MENEGHETTI, MORENO;
2004
Abstract
A series of metal complexes of tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine, [Py8TPyzPzH2], having the general formula [Py8TPyzPzM]âxH2O (M ) MgII(H2O), MnII, CoII, CuII, ZnII; x ) 3-8) were synthesized by reaction of the free-base macrocycle with the appropriate metal acetate in pyridine or dimethyl sulfoxide under mild conditions. Clathrated water and retained pyridine molecules for the MnII and CoII species are easily eliminated by heating under vacuum, the water molecules being recovered by exposure of the unsolvated macrocycles to air. Magnetic susceptibility measurements and EPR spectra of the materials in the solid state provide basic information on the spin state of the CuII, CoII, and MnII species. Colloidal solutions caused by molecular aggregation are formed in nondonor solvents (CH2Cl2, CHCl3), a moderately basic solvent (pyridine), and an acidic solvent (CH3COOH), with the extent of aggregation depending on the specific solvent and the central metal ion. UV-vis spectral monitoring of the solutions after preparation indicates that disaggregation systematically occurs as a function of time leading ultimately to the formation of clear solutions containing the monomeric form of the porphyrazine. Cyclic voltammetry and thin-layer spectroelectrochemistry show that each compound with an electroinactive metal ion undergoes four reversible one-electron reductions, leading to formation of the negatively charged species [Py8TPyzPzM]n- (n ) 1 - 4). The stepwise uptake of four electrons is consistent with a ring-centered reduction, but in the case of the cobalt complex a metal-centered (CoII f CoI) reduction occurs in the first process and only three additional reductions are observed. No oxidations are observed in pyridine or CH2Cl2 containing 0.1 M tetrabuthylammonium perchlorate (TBAP). The nonlinear optical properties (NLO) of the species [Py8TPyzPzM] (M ) 2HI, CuII, ZnII, MgII(H2O)) have also been examined with nanosecond pulses at 532 nm in dimethyl sulfoxide solution. Reverse saturable absorption is shown by all of the [Py8TPyzPzM] species, which exhibit distinct behavior depending on the nature of M and extent of aggregation.
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