The effect of ionic liquids on photoinduced electron-transfer reactions in a donor−bridge−acceptor system is examined for two ionic liquid solvents, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and tributylmethylammonium bis(trifluoromethylsulfonyl)amide. The results are compared with those for the same system in methanol and acetonitrile solution. Electron-transfer rates were measured using time-resolved fluorescence quenching for the donor− bridge−acceptor system comprising a 1-N,1-N-dimethylbenzene-1,4-diamine donor, a proline bridge, and a coumarin 343 acceptor. The photoinduced electron-transfer processes are in the inverted regime (−ΔG > λ) in all four solvents, with driving forces of −1.6 to −1.9 eV and estimated reorganization energies of about 1.0 eV. The observed electron-transfer kinetics have broadly distributed rates that are generally slower in the ionic liquids compared to the neutral solvents, which also have narrower rate distributions. To describe the broad distributions of electron-transfer kinetics, we use two different models: a distribution of exponential lifetimes and a discrete sum of exponential lifetimes. Analysis of the donor−acceptor electronic coupling shows that for ionic liquids this intramolecular electron-transfer reaction should be treated using a solvent-controlled electron-transfer model.

Photoinduced intramolecular charge separation across proline-bridged donor-acceptor complexes of the type Pyr-(Pro)n-DMPD (where Pyr=pyrene-1-sulfonyl and DMPD=N,N-dimethyl-1,4-phenylenediamine) was studied. The steady-state emission spectrum for n=0, 1, 2, 3 showed an increase in emission intensity with the number of proline residues. Time-dependent emission measured by streak camera showed increasing emission signal amplitude with increasing n, along with a decrease in decay rate. In all these studies, Pyr-Pro was used as a control complex for the decay of the excited pyrene acceptor moiety without the donor DMPD. Detailed photon counting experiments carried out in DMF/water, DMF, and toluene showed single-exponential kinetics for n=0, 1 and multiexponential kinetics for n=2, 3. Rate constants observed in DMF are for n=0, k=approximately 5x10(10) s(-1); n=1, k=9.70x10(8) s(-1); n=2, k=35.9x10(8) s(-1) (70%) and 5.58x10(8) s(-1) (30%); and n=3, k=16.6x10(8) s(-1) (55%) and 3.87x10(8) s(-1) (45%). These results show that a significant percentage of the n=2 and n=3 molecules undergo faster electron transfer than for the n=1 case. Conformational analysis for Pyr-(Pro)n-DMPD molecules in water showed that whereas only one conformation is possible for n=1, eight are possible for n=2, and 32 are possible for n=3. Calculation of the free energy and electronic coupling for these conformers in water showed that only a few of these conformations have the appropriate energy and electronic coupling to be observed in the experimental time window from 20 ps to 20 ns. Assignment of the conformers undergoing electron transfer in Pyr-(Pro)n-DMPD for n=2 and 3 was based on the values for the n=1 case, for which the measured rate constant is approximately 10(9) s(-1) and the calculated electronic coupling matrix element Hda is 297 cm(-1). The similarity in ground state energy between the cis and trans conformers for n=2 and 3, their use in aqueous-organic and organic solvents, and the nature of the Pyr and DMPD acceptor and donor groups could be contributing causes for the multiexponential kinetics, which was not observed for the metal ion derivatives of proline peptides studied earlier in aqueous solution.

Electronic coupling across peptide bonds has been determined throughout the peptide bond conformational space. Using the side chains of tyrosine (Tyr) and tryptophan (Trp) as donors (D) and acceptors (A), respectively, a plot of the electronic coupling matrix element H DA versus (ϕ,ψ) torsional angles has been constructed for Trp-peptide-Tyr molecules. The H DA values were obtained using the generalized Mulliken−Hush approach with electronic transition energies, permanent and transition dipole parameters derived from semiempirical quantum mechanical electronic structure calculations (INDO/S). The computed H DA values and the corresponding electron transfer (ET) rates show that specific helical peptide conformations situated in a narrow ϕ region of the full H DA-(ϕ,ψ) map play a significant role in developing strong electronic coupling for promoting ET. The H DA-(ϕ,ψ) map clearly defines the angular regions in space, where strong Trp-peptide-Tyr coupling occurs and peptide-mediated ET results, as well as regions of weak peptide coupling where the presence of the peptide has only marginal effects on electronic coupling.

Intramolecular photoinduced electron transfer from an N,N-dimethyl-p-phenylenediamine donor bridged by a diproline spacer to a coumarin 343 acceptor was studied using time-resolved fluorescence measurements in three ionic liquids and in acetonitrile. The three ionic liquids have the bis[(trifluoromethyl)sulfonyl]amide anion paired with the tributylmethylammonium, 1-butyl-1-methylpyrrolidinium, and 1-decyl-1-methylpyrrolidinium cations. The dynamics in the two-proline donor-bridge-acceptor complex are compared to those observed for the same donor and acceptor connected by a single proline bridge, studied previously by Lee et al. (J. Phys. Chem. C 2012, 116, 5197). The increased conformational freedom afforded by the second bridging proline resulted in multiple energetically accessible conformations. The multiple conformations have significant variations in donor-acceptor electronic coupling, leading to dynamics that include both adiabatic and nonadiabatic contributions. In common with the single-proline bridged complex, the intramolecular electron transfer in the two-proline system was found to be in the Marcus inverted regime.