Electron Spin-Dependent Electrocatalysis for the Oxygen Reduction Reaction in a Chiro-Self-Assembled Iron Phthalocyanine Device.

The chiral-induced spin selectivity effect (CISS) is a breakthrough phenomenon that has revolutionized the field of electrocatalysis. We report the first study on the electron spin-dependent electrocatalysis for the oxygen reduction reaction, ORR, using iron phthalocyanine, FePc, a well-known molecular catalyst for this reaction. The FePc complex belongs to the non-precious catalysts group, whose active site, FeN4, emulates catalytic centers of biocatalysts such as Cytochrome c. This study presents an experimental platform involving FePc self-assembled to a gold electrode surface using chiral peptides (L and D enantiomers), i.e., chiro-self-assembled FePc systems (CSAFePc). The chiral peptides behave as spin filters axial ligands of the FePc. One of the main findings is that the peptides' handedness and length in CSAFePc can optimize the kinetics and thermodynamic factors governing ORR. Moreover, the D-enantiomer promotes the highest electrocatalytic activity of FePc for ORR, shifting the onset potential up to 1.01 V vs. RHE in an alkaline medium, a potential close to the reversible potential of the O2 /H2 O couple. Therefore, this work has exciting implications for developing highly efficient and bioinspired catalysts, considering that, in biological organisms, biocatalysts that promote O2 reduction to water comprise L-enantiomers.

Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules.

We studied the electronic and conductance properties of two thiophene-curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO-LUMO band gap energies, showing that molecule 1 has lower values than 2. Theoretical calculations show the same trend. Self-assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO-LUMO gap in both molecules to almost the same value. Single-molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.

Control of single-molecule junction conductance of porphyrins via a transition-metal center.

Using scanning tunneling microscope break-junction experiments and a new first-principles approach to conductance calculations, we report and explain low-bias charge transport behavior of four types of metal-porphyrin-gold molecular junctions. A nonequilibrium Green's function approach based on self-energy corrected density functional theory and optimally tuned range-separated hybrid functionals is developed and used to understand experimental trends quantitatively. Importantly, due to the localized d states of the porphyrin molecules, hybrid functionals are essential for explaining measurements; standard semilocal functionals yield qualitatively incorrect results. Comparing directly with experiments, we show that the conductance can change by nearly a factor of 2 when different metal cations are used, counter to trends expected from gas-phase ionization energies which are relatively unchanged with the metal center. Our work explains the sensitivity of the porphyrin conductance with the metal center via a detailed and quantitative portrait of the interface electronic structure and provides a new framework for understanding transport quantitatively in complex junctions involving molecules with localized d states of relevance to light harvesting and energy conversion.