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Long-range exchange contribution to singlet-singlet energy transfer in a series of rigid bichromophoric molecules

✍ Scribed by Henk Oevering; Jan W. Verhoeven; Michael N. Paddon-Row; Evangelo Cotsaris; Noel S. Hush

Publisher: Elsevier Science
Year: 1988
Tongue: English
Weight: 647 KB
Volume: 143
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(88)87401-3

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✦ Synopsis

Intramolecular singlet-singlet energy transfer is reported in a series of compounds containing a 1,4-dimethoxy-naphthalene chromophore as the energy donor and a cyclic ketone as the energy acceptor connected by rigid, elongated, saturated hydrocarbon bridges with an effective length of 4,6, and 8 C-C o bonds. The rate of energy transfer is found to be proportional to the spectral overlap -as varied by solvent variationand to show an exponential distance dependence while its magnitude significantly exceeds that predicted for a dipole-dipole coupling mechanism. From this it is concluded that energy transfer occurs predominantly via an exchange mechanism. Exchange integrals of 60, 10, and 2.5 cm-' across 4, 6, and 8 o bonds are calculated. The magnitude of these is proposed to signify through-bond exchange interaction between symmetry-matched donor (KX*) and acceptor (nx*) states.

📜 SIMILAR VOLUMES

Comment on “long-range exchange contribu

Comment on “long-range exchange contribution to singlet-singlet energy transfer in a series of rigid bichromophoric molecules”, chem. phys. letters 143 (1988) 488

✍ Shammai Speiser; Mordecai B. Rubin 📂 Article 📅 1988 🏛 Elsevier Science 🌐 English ⚖ 114 KB

We point out earlier work on intramolecular electronic energy tranfer in bichromophoric molecules and the possibility of an alternative interpretation of the results of Oevering, Verhoeven, Paddon-Row, Cotsaris and Hush.

On a long-range exchange mechanism for e

On a long-range exchange mechanism for energy transfer in rigid bichromophoric molecules

✍ Henk Oevering; Jan W. Verhoeven; Michael N. Paddon-Row; Evangelo Cotsaris; Noel 📂 Article 📅 1988 🏛 Elsevier Science 🌐 English ⚖ 108 KB

The comment of Speiser and Rubin regarding the impossibility of long-range, intramolecular exchange energy transfer is refuted by comparison with recent data for other phenomena, e.g. electron transfer, that depend upon electronic interaction between nonconjugatively connected chromophores.