Charge Transfer-Induced Weakening of Vibronic Coupling for Single Terrylene Molecules Adsorbed onto Hexagonal Boron Nitride.

Fluorescence spectra of single terrylene molecules adsorbed on hexagonal boron nitride flakes were recorded at cryogenic temperatures. The pure electronic transitions of terrylene molecules are spread over a broad energy scale from 570 to 610 nm. Surprisingly, peaks in the vibrationally resolved fluorescence spectrum show intensity variations of ≤20-fold between molecules.

Limiting Molecular Twisting: Upgrading a Donor-Acceptor Dye to Drive H Evolution.

The donor-acceptor (D-A) dye 4-(bis-4-(5-(2,2-dicyano-vinyl)-thiophene-2-yl)-phenyl-amino)-benzoic acid (P1) has been frequently used to functionalize NiO photocathodes and induce photoelectrochemical reduction of protons when coupled to a suitable catalyst. Photoinduced twisting of the P1 dye is steered on NiO by co-adsorption of tetradecanoic acid (C, myristic acid (MA)). Density Functional Theory and time-resolved photoluminescence studies confirm that twisting lowers the energy levels of the photoexcited D-A dye.

Effect of Anchoring Dynamics on Proton-Coupled Electron Transfer in the Ru(bda) Coordination Oligomer on a Graphitic Surface.

The oligomeric ruthenium-based water oxidation catalyst, Ru(bda), is known to be experimentally anchored on graphitic surfaces through CH-π stacking interactions between the auxiliary bda ([2,2'-bipyridine]-6,6'-dicarboxylate) ligand bonded to ruthenium and the hexagonal rings of the surface. This anchoring provides control over their molecular coverage and enables efficient catalysis of water oxidation to dioxygen. The oligomeric nature of the molecule offers multiple anchoring sites at the surface, greatly enhancing the overall stability of the hybrid catalyst-graphitic surface anode through dynamic bonding.

Observation of Dark States in Two-Dimensional Electronic Spectra of Chlorosomes.

Observations of low-lying dark states in several photosynthetic complexes challenge our understanding of the mechanisms behind their efficient energy transfer processes. Computational models are necessary for providing novel insights into the nature and function of dark states, especially since these are not directly accessible in spectroscopy experiments. Here, we will focus on signatures of dark-type states in chlorosomes, a light-harvesting complex from green sulfur bacteria well-known for uniting a broad absorption band with very efficient energy transfer.

An integrated approach towards extracting structural characteristics of chlorosomes from a mutant of .

Chlorosomes, the photosynthetic antenna complexes of green sulfur bacteria, are paradigms for light-harvesting elements in artificial designs, owing to their efficient energy transfer without protein participation. We combined magic angle spinning (MAS) NMR, optical spectroscopy and cryogenic electron microscopy (cryo-EM) to characterize the structure of chlorosomes from a mutant of . The chlorosomes of this mutant have a more uniform composition of bacteriochlorophyll (BChl) with a predominant homolog, [8Ethyl, 12Ethyl] BChl , compared to the wild type (WT).