ESR and electronic spectral investigation of the self-association of phthalocyanine dyes in solution

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<jats:p>The degree of molecular association of a copper phthalocyanine dye in benzene and tetrahydrofuran has been studied by electronic spectroscopy and ESR. Electronic spectroscopy in the visible spectral region demonstrates the existence of monomer-dimer equilibria in the 10−6–10−3 M concentration range. The dimerization constants Keq=Cd/Cm2 are (1.58± 0.09)× 104M−1 and (1.41± 0.50)× 102M−1 at room temperature in benzene and tetrahydrofuran, respectively. The ESR envelope spectra are found to vary systematically in the same concentration range as a function of solvent at fixed temperature. To deduce the manner in which aggregation in these solvents influences the detailed features of the ESR envelope spectrum, it is found useful to follow the evolution of envelope lineshape in copper phthalocyanine-metal-free phthalocyanine solid solutions as the concentration of copper phthalocyanine is progressively increased. The principal effect is found to be the perturbing influence of intermolecular copper exchange interactions in averaging local hyperfine fields, a process which can be both computer simulated and followed directly in the experimental spectra.</jats:p>

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