Michael Lesslie

Electron-Rotor Interaction in Organic-Inorganic Lead Iodide Perovskites Discovered by Isotope Effects.

We report on the carrier-rotor coupling effect in perovskite organic-inorganic hybrid lead iodide (CH3NH3PbI3) compounds discovered by isotope effects. Deuterated organic-inorganic perovskite compounds including CH3ND3PbI3, CD3NH3PbI3, and CD3ND3PbI3 were synthesized. Devices made from regular CH3NH3PbI3 and deuterated CH3ND3PbI3 exhibit comparable performance in band gap, current-voltage, carrier mobility, and power conversion efficiency. However, a time-resolved photoluminescence (TRPL) study reveals that CH3NH3PbI3 exhibits notably longer carrier lifetime than that of CH3ND3PbI3, in both thin-film and single-crystal formats. Furthermore, the comparison in carrier lifetime between CD3NH3PbI3 and CH3ND3PbI3 single crystals suggests that vibrational modes in methylammonium (MA(+)) have little impact on carrier lifetime. In contrast, the fully deuterated compound CD3ND3PbI3 reconfirmed the trend of decreasing carrier lifetime upon the increasing moment of inertia of cationic MA(+). Polaron model elucidates the electron-rotor interaction.

Cytosine radical cation: a gas‐phase study combining IRMPD spectroscopy, UV‐PD spectroscopy, ion‐molecule reactions, and theoretical calculations

The radical cation of cytosine (Cyt.+ ) is generated by dissociative oxidation from a ternary CuII complex in the gas phase. The radical cation is characterized by infrared multiple photon dissociation (IRMPD) spectroscopy in the fingerprint region, UV/Vis photodissociation (UVPD) spectroscopy, ion-molecule reactions, and theoretical calculations (density functional theory and ab initio). The experimental IRMPD spectrum features diagnostic bands for two enol-amino and two keto-amino tautomers of Cyt.+ that are calculated to be among the lowest energy isomers, in agreement with a previous study. Although the UVPD action spectrum can also be matched to a combination of the four lowest energy tautomers, the presence of a nonclassical distonic radical cation cannot be ruled out. Its formation is, however, unlikely due to the high energy of this isomer and the respective ternary CuII complex. Gas-phase ion-molecule reactions showed that Cyt.+ undergoes hydrogen-atom abstraction from 1-propanethiol, radical recombination reactions with nitric oxide, and electron transfer from dimethyl disulfide.

The influence of fluoroalkyl chains in redox electrolytes for energy conversion

We discovered an unprecedented fundamental interaction originated from the fluoroalkyl chains at the interface between light harvesting chromophore and charge transport redox electrolyte in dye-sensitized solar cells (DSSCs). A fluoroalkylated Ru complexes dye (FN719) was synthesized and upon anchoring on nanoparticulate TiO2 electrodes, FN719 exhibits 5 times better photostability in humid air than that of the conventional N719 due to the hydrophobicity of the fluoroalkyl chains. Moreover, the lipophobicity of fluoroalkylated chains in organic electrolyte causes a size-selective steric hindrance with respect to the redox couple I−/I3−, leading to a more stalled diffusion of the bulky I3− towards dyes and TiO2 photoanode than that of the lean I−. As such, without sacrificing the forward electron transport and quantum efficiency, the recombination in FN719-based DSSCs is suppressed to be 1.3 times slower than N719-based DSSCs studied by the photovoltage transients and electrochemical impedance spectroscopy...

Alkali-Metal-Ion-Assisted Hydrogen Atom Transfer in the Homocysteine Radical

Intramolecular hydrogen atom transfer (HAT) was examined in homocysteine (Hcy) thiyl radical/alkali metal ion complexes in the gas phase by combination of experimental techniques (ion-molecule reactions and infrared multiple photon dissociation spectroscopy) and theoretical calculations. The experimental results unequivocally show that metal ion complexation (as opposed to protonation) of the regiospecifically generated Hcy thiyl radical promotes its rapid isomerisation into an α-carbon radical via HAT. Theoretical calculations were employed to calculate the most probable HAT pathway and found that in alkali metal ion complexes the activation barrier is significantly lower, in full agreement with the experimental data. This is, to our knowledge, the first example of a gas-phase thiyl radical thermal rearrangement into an α-carbon species within the same amino acid residue and is consistent with the solution phase behaviour of Hcy radical.

Gas-phase tyrosine-to-cysteine radical migration in model systems

Radical migration, both intramolecular and intermolecular, from the tyrosine phenoxyl radical Tyr(O•) to the cysteine radical Cys(S•) in model peptide systems was observed in the gas phase. Ion–molecule reactions (IMRs) between the radical cation of homotyrosine and propyl thiol resulted in a fast hydrogen atom transfer. In addition, radical cations of the peptide LysTyrCys were formed via two different methods, affording regiospecific production of Tyr(O•) or Cys(S•) radicals. Collision-induced dissociation of these isomeric species displayed evidence of radical migration from the oxygen to sulfur, but not for the reverse process. This was supported by theoretical calculations, which showed the Cys(S•) radical slightly lower in energy than the Tyr(O•) isomer. IMRs of the LysTyrCys radical cation with allyl iodide further confirmed these findings. A mechanism for radical migration involving a proton shuttle by the C-terminal carboxylic group is proposed.