Terms Of Through-bond Interactions Research Articles

Time-resolved analysis of intramolecular electronic energy transfer in methylenes-linked naphthalene–anthracene compounds in solution and in stretched polymer films

Intramolecular electronic energy transfer in methylenes-linked naphthalene and anthracene (referred to as AnN, n=1, 3 and 6 denoting number of methylene units) was examined by time-correlated single-photon counting technique in n-hexane and in stretched PVA films. The energy transfer rates in A1N, A3N and A6N in solution were measured and the chain length dependence of these rate constants is discussed in terms of through-bond interaction via the connecting bridge, in addition to direct Coulombic interaction.

Time-resolved analysis of intramolecular electronic energy transfer in methylenes-linked naphthalene–anthracene compounds

The mechanism of intramolecular electronic energy transfer (EET) in methylene-linked naphthalene and anthracene (referred to as A nN, n=1, 3 and 6) was examined by time-correlated single-photon counting technique. The chain length dependence of measured EET rate constants is explained in terms of through-bond interaction via the connecting bridge, besides direct Coulombic interaction. In addition, intramolecular energy transfer in A1N and A3N may compete with vibrational relaxation of the corresponding vibrational level of the excited anthracene moiety by comparing the time-resolved spectra of A1N, A3N and A6N.

On the physical interpretation of through-bond interactions: A coupled-chromophore model for π-electron photoionization of non-conjugated dienes

A coupled-chromophore model is presented to explain the splittings of the photoelectron energies arising in the photoionization of the π-electrons in non-conjugated dienes. The predictions of the model are consistent with the experimental splittings for a range of dienes, and suggest that the σ framework plays no physical role in coupling the two chromophores. The implications for the physical interpretation in terms of through-bond interactions are discussed.

Photoelectron Spectra of the cis- and trans-Isomers of Some Ethylene Derivatives

Abstract The photoelectron spectra of cis- and trans-stilbenes, fumaric acid, dimethyl maleate, and dimethyl fumarate were measured and interpreted, special attention being paid upon their difference between the corresponding trans- and cis-isomers. The two characteristics were found for the photoelectron spectra of cis- and trans-stilbenes: (1) the splitting between the first and fifth bands is smaller for the cis-isomer (steric-hindrance effect); (2) the splitting between the second and third bands is larger for the cis-isomer (through-space interaction). The difference in the carbonyl n orbital ionization potentials between dimethyl maleate and fumarate was interpreted in terms of through-bond interaction.