2004
DOI: 10.1021/jp030953u
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Abstract: A combination of theory and experiment is used to identify a novel variable excitonic coupling in a series of building blocks for small phenylacetylene dendrons. Systematic changes in the experimental emission spectra, radiative lifetimes, and polarization anisotropies as the number of meta-conjugated branches increases provide evidence for a qualitative change in the electronic structure in the relaxed excited state. The excited state electronic structure is investigated theoretically using ab initio CASSCF a… Show more

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Cited by 118 publications
(135 citation statements)
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“…Similar geometric relaxation effects resulting from partial cancellation between TB and TS interactions have been reported in meta-linked phenylene-based oligomers. [13] We are now prepared to discuss the nature of the electronic coupling mediating excitation motion in PPE. As described above, in the weak coupling limit relevant here, energy diffusion occurs via a sequence of hopping steps taking place after geometric relaxation on the donor.…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…Similar geometric relaxation effects resulting from partial cancellation between TB and TS interactions have been reported in meta-linked phenylene-based oligomers. [13] We are now prepared to discuss the nature of the electronic coupling mediating excitation motion in PPE. As described above, in the weak coupling limit relevant here, energy diffusion occurs via a sequence of hopping steps taking place after geometric relaxation on the donor.…”
Section: Resultsmentioning
confidence: 99%
“…For all coupling strengths, the singlet electronic excited-state wavefunctions of these bi-chromophoric systems can be expanded in a basis including the localized excitations over the two chromophores (j1 Ã 2> and j12 Ã >) and the charge-transfer configurations among them (j1 þ 2 À > and j1 À 2 þ >). As described by Scholes et al [12] and Thompson et al, [13] these electronic configurations mix together in the bi-chromophore via either purely covalent (<1 Ã 2jHj12 Ã >), ionic (<1 þ 2 À jHj 1 À 2 þ >) or mixed-type (e.g., <1 Ã 2j Hj1 þ 2 À >) interactions (with H the inter-chromophore Hamiltonian). These couplings can be partitioned into a long-range Coulomb contribution that is operative provided spin selection rules are obeyed and short-range contributions that invoke direct overlap between the wavefunctions of the two chromophores.…”
Section: Full Papermentioning
confidence: 95%
“…This effect in the triaryl core is likely due to the meta positions of the three benzene rings, which breaks the conjugation. [163,[303][304][305] Finally, the solvatochromic behavior of branched systems built from the dipolar arms has been found to be correlated to the TPA amplitudes [123] (not discussed in this review for the sake of conciseness). This is related to the intramolecular charge transfer character of the transitions and suggests that the solvatochromic behavior may provide a qualitative estimate of the TPA performance of such chromophores.…”
Section: Branching Of Dipoles: Triphenylbenzene Derivativesmentioning
confidence: 99%
“…This observation is significant because it shows that these entirely conjugated systems can demonstrate novel photophysical phenomena, e.g. new states not visible in the absorption spectrum but which can be harnessed to improve light harvesting in engineered molecules [2]. interesting from the standpoint of its unique photophysics, it probably does not present a viable long-term solution to the problem of light-harvesting for organic solar cells [12].…”
Section: ) Energy Transfer In Phenylene Ethynylene Dendrimersmentioning
confidence: 99%