Anisotropic materials made from stacked macrocycles have potential applications as organic conductors and nonlinear optical materials. Using self-consistent-field local density theory, we have been exploring the ground and excited state electronic structures of metal substituted tetraazaporphyrins, phthalocyanines, and tetrabenzoporphyrins. The calculated and measured polarized optical absorption peaks are in satisfactory agreement. The theoretical dipole oscillator strengths provide absolute intensities for verification of transition assignments, which are helpful for identifying low-lying states and excitation mechanisms.
First principles density functional theory is utilized to describe electronic structure and magnetic interactions
between Cr(III) ions in linear and bent geometry of [cis-[hydroxotetramminechromium-μ-hydroxopentamminechromium]4+. The effective exchange parameter J is extracted and compared with empirical values fitted to
experimental data. The calculated value J = 48 K for bent geometry compares well with the 30 K experimental
value; the magnetic interaction is an order of magnitude larger in the linear configuration. Low-lying optical
transitions are analyzed, making use of the transition state scheme, and are in semiquantitative agreement with
experimental absorption.
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