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Spectroscopic Studies of Bridge Contributions to Electronic Coupling in a Donor-Bridge-Acceptor Biradical System
journal contribution
posted on 2016-02-20, 22:09 authored by Martin L. Kirk, David A. Shultz, Ezra C. Depperman, Diana Habel-Rodriguez, Robert D. SchmidtVariable-temperature electronic absorption and resonance
Raman spectroscopies are used to probe the excited state electronic
structure of TpCum,MeZn(SQ-Ph-NN) (1), a donor-bridge-acceptor (D-B-A) biradical complex and
a ground state analogue of the charge-separated excited state formed
in photoinduced electron transfer reactions. Strong electronic coupling mediated by the p-phenylene
bridge stabilizes the triplet ground state of this molecule. Detailed
spectroscopic and bonding calculations elucidate key bridge distortions
that are involved in the SQ(π)SOMO → NN-Ph
(π*)LUMO D → A charge transfer (CT) transition.
We show that the primary excited state distortion that accompanies
this CT is along a vibrational coordinate best described as a symmetric
Ph(8a) + SQ(in-plane) linear combination and underscores the dominant
role of the phenylene bridge fragment acting as an electron acceptor
in the D-B-A charge transfer state. Our results show the importance
of the phenylene bridge in promoting
(1) electron transfer in D-Ph-A systems and (2) electron transport
in biased electrode devices that employ a 1,4-phenylene linkage. We
have also developed a relationship between the spin density on the
acceptor, as measured via the isotropic NN nitrogen hyperfine interaction,
and the strength of the D → A interaction given by the magnitude
of the electronic coupling matrix element, Hab.
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Spectroscopic Studiescalculations elucidateresults showcharge transferphotoinduced electron transfer reactionsstate distortionphenylene bridge fragmentphenylene bridgeNN nitrogenLUMOelectron acceptormatrix elementBridge Contributionselectrode devicestriplet ground statebridge distortionsCTSQground state analogueresonance Raman spectroscopies
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