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Porphyrins XXVIII. Extended Hückel calculations on metal phthalocyanines and tetrazaporphins

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Abstract

Extended Hückel (EH) calculations on Mg, Zn, Cu, Ni, Fe, Mn, and VO complexes of phthalocyanine and tetrazaporphin are reported and the results compared to similar calculations on porphyrins. The smaller ring size of phthalocyanine gives rise to a larger ligand field. The bridge nitrogen atoms give rise to n - π * transitions, which are probably in the region of the Soret band. In Ni, Co, Fe, and Mn there is strong mixing of the bridge N2p σ and metal b 2g (d xy ), which should affect the ligand field. Extra absorption bands observed in the near uv of NiPc and CoPc are attributed to d π → π * transitions. A general symmetrized EH program is reported that speeds calculations on large systems.

Zusammenfassung

Für die Komplexverbindungen von Mg, Zn, Cu, Ni, Fe, Mn und Vo mit Phtalocyanin und Tetrazaporphin werden erweiterte Hückelrechnungen (EH) durchgeführt und die Ergebnisse mit ähnlichen Berechnungen an Porphyrinen verglichen. Die geringere Ringgröße des Phtalocyanins gibt Anlaß zu einem größeren Ligandenfeld. Das Brücken-Stickstoffatom gibt Anlaß zu n-π *-Übergängen, die wahrscheinlich im Gebiet der Soret-Bande liegen. Beim Ni, Co, Fe und Mn tritt eine starke Mischung der Orbitale des Brückenstickstoff-Atoms N2p σ und b 2g (d xy ) auf, die das Ligandenfeld beeinflussen sollte. Die zusätzlichen Absorptionsbanden, die im nahen UV bei NiPc und CoPc beobachtet werden, werden d π → π *-Übergängen zugeordnet. Ein allgemeines, symmetrisiertes EH-Programm wird mitgeteilt, das die Berechnung großer Systeme beschleunigt.

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Authors and Affiliations

  1. Department of Chemistry, University of Washington, 98195, Seattle, Washington

    Arnold M. Schaffer, Martin Gouterman & Ernest R. Davidson

  2. Department of Chemistry, University of Houston, 77004, Houston, Texas, USA

    Arnold M. Schaffer

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  1. Arnold M. Schaffer
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  2. Martin Gouterman
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  3. Ernest R. Davidson
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Additional information

Paper XXVII. M. Gouterman, F. P. Schwarz, P. D. Smith, and D. Dolphin, J. chem. Physics, in press (1973).

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Schaffer, A.M., Gouterman, M. & Davidson, E.R. Porphyrins XXVIII. Extended Hückel calculations on metal phthalocyanines and tetrazaporphins. Theoret. Chim. Acta 30, 9–30 (1973). https://doi.org/10.1007/BF00527632

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