Superexchange contributions to distance dependence of electron transfer/transport: exchange and electronic coupling in oligo(para-phenylene)- and oligo(2,5-thiophene)-bridged donor-bridge-acceptor biradical complexes.

The preparation and characterization of three new donor-bridge-acceptor biradical complexes are described. Using variable-temperature magnetic susceptibility, EPR hyperfine coupling constants, and the results of X-ray crystal structures, we evaluate both exchange and electronic couplings as a function of bridge length for two quintessential molecular bridges: oligo(para-phenylene), ß = 0.39 Å(-1) and oligo(2,5-thiophene), ß = 0.22 Å(-1). This report represents the first direct comparison of exchange/electronic couplings and distance attenuation parameters (ß) for these bridges. The work provides a direct measurement of superexchange contributions to ß, with no contribution from incoherent hopping. The different ß values determined for oligo(para-phenylene) and oligo(2,5-thiophene) are due primarily to the D-B energy gap, Δ, rather than bridge-bridge electronic couplings, H(BB). This is supported by the fact that the H(BB) values extracted from the experimental data for oligo(para-phenylene) (H(BB) = 11,400 cm(-1)) and oligo(2,5-thiophene) (12,300 cm(-1)) differ by <10%. The results presented here offer unique insight into the intrinsic molecular factors that govern H(DA) and ß, which are important for understanding the electronic origin of electron transfer and electron transport mediated by molecular bridges.

Donor-acceptor biradicals as ground state analogues of photoinduced charge separated states.

A Valence Bond Configuration Interaction (VBCI) model is used to relate the intraligand magnetic exchange interaction (J) to the electronic coupling matrix element (HAB) in Tp(Cum,MeZn)(SQNN), a compound that possesses a Donor-Acceptor (D-A) SemiQuinone-NitronylNitroxide (SQNN) biradical ligand. Within this framework, an SQ --> NN charge transfer state mixes with the ground state and stabilizes the spin triplet (S = 1). This charge-transfer transition is observed spectroscopically and probed using resonance Raman spectroscopy. In addition, the temperature-dependent electronic absorption spectrum of the Ni(II) complex, Tp(Cum,MeNi)(SQNN), has been studied. Exchange coupling between the S = 1 Ni(II) ion and S = 1 SQNN provides a mechanism for observing the formally spin-forbidden, ligand-based 3GC --> 1CTC transition. This provides a means of determining U, the mean GC --> CTC energy, and a one-center exchange integral, K(0). The experimental determination of J, U, and K(0) permits facile calculation of HAB, and we show that this methodology can be extended to determine the electronic coupling matrix element in related SQ-Bridge-NN molecules. As magnetic susceptibility measurements are easily acquired in the solid state, H(AB) may be effectively determined for single molecules in a known geometry, provided a crystal structure exists for the biradical complex. Thus, SQ-Bridge-NN molecules possess considerable potential for probing both geometric and electronic structure contributions to the magnitude of the electronic coupling matrix element associated with a given bridge fragment.