title: Hyperfine interaction, spin polarization, and spin delocalization as probes of donor-bridge-acceptor interactions in exchange-coupled biradicals.
abstract: Computations and EPR spectroscopy are used to probe the spin distribution of donor-bridge-acceptor (D-B-A) biradical complexes: Tp(Cum,Me)Zn(SQ-NN) (1), Tp(Cum,Me)Zn(SQ-1,4-Ph-NN) (2), Tp(Cum,Me)Zn(SQ-2,5-TP-NN) (3), and Tp(Cum,Me)Zn(SQ-2,5-Xyl-NN) (4) (SQ = orthosemiquinone and NN = nitronylnitroxide). These complexes are ground-state analogs of the charge-separated excited states formed in photoinduced electron transfer reactions. The intraligand magnetic exchange interaction (J) in these complexes is mediated by the bridges and has been found to stabilize the triplet ground states of 1 and 2. Detailed spectroscopic and bonding calculations have been used to elucidate the role of the bridge fragment (B) and its conformation relative to donor (SQ) and acceptor (NN) on spin density distributions. The computed results correlate well with experimental nitrogen hyperfine coupling constants.
authors.affiliation: Department of Chemistry and Chemical Biology, The University of New Mexico, MSC03 2060, Albuquerque, New Mexico 87131-0001, USA.
authors.forename: Martin L
authors.initials: ML
authors.lastname: Kirk
authors.forename: David A
authors.initials: DA
authors.lastname: Shultz
authors.forename: Diana
authors.initials: D
authors.lastname: Habel-Rodriguez
authors.forename: Robert D
authors.initials: RD
authors.lastname: Schmidt
authors.forename: Ubie
authors.initials: U
authors.lastname: Sullivan