Tetraazaporphyrins (TAPs), phthalocyanines (Pcs), naphthalocyanines (Ncs), and anthracocyanines (Acs) with four tert-butyl groups attached at similar positions have been synthesized, and their electronic absorption, magnetic circular dichroism (MCD), IR, and voltammetric properties were studied and interpreted with the help of quantum-mechanical calculations. Through the preparation of a series of compounds with the same number of the same substituent, the effects of the increase in the size of the ring system were clearly derived. The main results may be summarized as follows. 1) The Q band shifts to longer wavelength and its intensity increases, but with decreasing degree of change with increasing molecular size. If the size of the effect of benzene directly fused to the TAP skeleton is set at unity, the effects of the second and third benzene units are roughly 0.8 and 0.5, respectively. 2) The splitting of the Q bands in metal-free compounds decreases with increasing molecular size, so that the Q bands of H2Nc and H2Ac appear as single bands. 3) The magnitude of the orbital angular momentum of the excited state of the ligand decreases with increasing molecular size. 4) Interestingly, the ring current, as judged from the positions of pyrrole proton signals in the 1H NMR spectrum, appears to decrease with increasing molecular size. 5) The first reduction potential becomes less negative, but only slightly, whereas the first oxidation potential shows a marked shift to less positive values with increasing molecular size, indicating that the HOMO destabilizes significantly as the molecule becomes larger. 6) In 5), the extent of the HOMO destabilization with molecular size differs depending on the central metal, so metals producing smaller destabilization effects can allow larger macrocycles. Of the metals studied, the most effective is cobalt, and the practical size limit is represented by the Acs. 7) The IR spectra become simpler the larger the molecule, and the main bands were assigned by DFT calculations. 8) The trend in experimentally determined redox potentials and electronic absorption and MCD spectra were reasonably reproduced by MO calculations using the ZINDO/S Hamiltonian. 9) EPR data for several metallocomplexes are also reported.

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