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Crystalline Molecular Complexes and CompoundsStructures and Principles$
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Frank H. Herbstein

Print publication date: 2005

Print ISBN-13: 9780198526605

Published to Oxford Scholarship Online: September 2007

DOI: 10.1093/acprof:oso/9780198526605.001.0001

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Charge transfer molecular compounds with delocalized π-π* interaction - introduction and general survey

Charge transfer molecular compounds with delocalized π-π* interaction - introduction and general survey

Chapter:
(p.925) Chapter 13 Charge transfer molecular compounds with delocalized π-π* interaction - introduction and general survey
Source:
Crystalline Molecular Complexes and Compounds
Author(s):

Frank H. Herbstein

Publisher:
Oxford University Press
DOI:10.1093/acprof:oso/9780198526605.003.0013

About one hundred years elapsed between the preparation of the first crystalline charge transfer molecular compound with delocalized π-π* interaction (anthracene...picric acid) and the development of a generally-accepted theory based on the experimental demonstration that these compounds crystallized in mixed stacks with alternation of donor and acceptor moieties. The conditions under which the moieties occur as neutral molecules (the predominant situation) or as radical ions have been defined. The properties of a donor-acceptor π-compound depend on the individual properties of the donor and acceptor participants, usually expressed in terms of donor ionization potential and acceptor electron affinity as modified for the difference between the gas and crystalline phases. These crystalline binary sytems should be characterized in terms of their binary phase diagrams, which will show the appearance of DnAm compounds, where ‘n’ and ‘m’ are usually but not always 1. These principles can be extended to self-complexes, where donor and acceptor portions are situated within the same molecule.

Keywords:   donor and acceptor components, ionization potential, electron affinity, binary phase diagrams, self-complexes

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