Abstract
Structure-property relationships of conjugated organic compounds are governed by three fundamental principles, the triad principle, the energy principle, and the bonding principle, which enable chemists to design new substances with given properties. Especially color and constitution relationships are understood by five basic color rules which states that polymethine-like compounds absorb at much longer wavelengths than aromatic or polyene-like compounds of the same size. Further strong red-shift necessitates perturbation of the unique alternation of the n-electron densities in polymethines. As the intended red-shifts are compensated through aromatization and polyene formation such effects have to be excluded in molecular engineering of NIR dyes.
More quantitative estimations of structure-property relationships are achieved through long polymethine chain approximation (LPCA) which is a topological approach involving effective parameters of polymethine chain end groups, namely, the electron donor ability, the effective length, and their derivatives with respect to energy.
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Daehne, S., Dekhtyar, M.L. (1998). Molecular Engineering of NIR Dyes. In: Daehne, S., Resch-Genger, U., Wolfbeis, O.S. (eds) Near-Infrared Dyes for High Technology Applications. NATO ASI Series, vol 52. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-5102-3_17
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DOI: https://doi.org/10.1007/978-94-011-5102-3_17
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