Spectroscopic Studies of Bridge Contributions to Electronic Coupling in a Donor-Bridge-Acceptor Biradical System

Variable-temperature electronic absorption and resonance Raman spectroscopies are used to probe the excited state electronic structure of Tp<sup>Cum,Me</sup>Zn­(SQ-<i>Ph</i>-NN) (<b>1</b>), 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 <i>p</i>-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)<sub>SOMO</sub> → NN-Ph (π*)<sub>LUMO</sub> 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, <i>H</i><sub><i>ab</i></sub>.