Poly(dehydroalanine)-Based Hydrogels as Efficient Soft Matter Matrices for Light-Driven Catalysis.

Soft matter integration of photosensitizers and catalysts provides promising solutions to developing sustainable materials for energy conversion. Particularly, hydrogels bring unique benefits, such as spatial control and 3D-accessibility of molecular units, as well as recyclability. Herein, the preparation of polyampholyte hydrogels based on poly(dehydroalanine) (PDha) is reported. Chemically crosslinked PDha with bis-epoxy poly(ethylene glycol) leads to a transparent, self-supporting hydrogel. Due to the ionizable groups on PDha, this 3D polymeric matrix can be anionic, cationic, or zwitterionic depending on the pH value, and its high density of dynamic charges has a potential for electrostatic attachment of charged molecules. The integration of the cationic molecular photosensitizer [Ru(bpy)3 ]2+ (bpy = 2,2'-bipyridine) is realized, which is a reversible process controlled by pH, leading to light harvesting hydrogels. They are further combined with either a thiomolybdate catalyst ([Mo3 S13 ]2- ) for hydrogen evolution reaction (HER) or a cobalt polyoxometalate catalyst (Co4 POM = [Co4 (H2 O)2 (PW9 O34 )2 ]10- ) for oxygen evolution reaction (OER). Under the optimized condition, the resulting hydrogels show catalytic activity in both cases upon visible light irradiation. In the case of OER, higher photosensitizer stability is observed compared to homogeneous systems, as the polymer environment seems to influence decomposition pathways.

Neutral, Heteroleptic [Cu(I)(PPh3 )2 (4H-imidazolato)] Complexes: Ligand Exchange Reactivity, Redox Properties, Excited-State Dynamics.

Cu(I) 4H-imidazolate complexes are rare examples of Cu(I) complexes with chelating anionic ligands and are potent photosensitizers with unique absorption and photoredox properties. In this contribution, five novel heteroleptic Cu(I) complexes with monodentate triphenylphosphine co-ligands are investigated. As a consequence of the anionic 4H-imidazolate ligand and in contrast to comparable complexes with neutral ligands, these complexes are more stable than their homoleptic bis(4H-imidazolato)Cu(I) congeners. Here, the ligand exchange reactivity was studied by 31 P-,19 F-, and variable temperature NMR and the ground state structural and electronic properties by X-ray diffraction, absorption spectroscopy, and cyclic voltammetry. The excited-state dynamics were investigated by femto- and nanosecond transient absorption spectroscopy. The observed differences, with respect to chelating bisphosphine bearing congeners, are often due to the increased geometric flexibility of the triphenylphosphines. These observations render the investigated complexes interesting candidates for photo(redox)reactions not accessible with chelating bisphosphine ligands.

Understanding charge carrier dynamics in a P3HT:FLR blend.

In organic semiconductors, optical absorption is pivotal for the performance of optoelectronic devices. The absorption by the semiconductors generates excitons which dissociate into free charge carriers, resulting in energy conversion. Although high performance has been achieved in non-fullerene organic solar cells, their charge generation behavior is far from being well understood. Keeping this in view, we have employed optical spectroscopic tools to study the charge generation mechanism in FLR (1,6,7,10-tetramethylfluoranthene) as a non-fullerene electron acceptor blended with P3HT (poly(3-hexylthiophene)) as an electron donor in five different solvents. Through steady state UV-visible and photoluminescence spectroscopy, we provide a basic understanding of charge transport by enlightening the influence of solvents on the aggregation behavior and exciton bandwidth. Furthermore, for the first time, by employing ultrafast vis-NIR transient absorption spectroscopy, we address the ultrafast charge generation and charge separation mechanism with systematic variation in solvent polarity by incorporating the time evolution of the transient species under various pump-probe wavelengths in the range of 450 nm to 1600 nm. For the different excitation wavelengths, the lifetime kinetics have been depicted by their multiexponential fits. The results show a fast decay term at a lifetime of a few picoseconds (ps) (∼1 to 5 ps) and a slow decay term at a lifetime of ∼500 ps. The charge generation in the P3HT:FLR blend proceeds on a ps time scale, which implies good intermixing of the components. It is clearly established that the non-halogenated solvents influence this aggregation behavior and higher conjugation lengths with higher photoluminescence quenching contribute to the higher charge generation. The enhanced polaron population in P3HT with the addition of FLR illustrates the importance of this acceptor material in the blend because a good solvent-material combination is essential to enhance the charge generation. As such, this comprehensive study explicitly shows the role of FLR as an emerging efficient non-fullerene acceptor for further improving the performance of devices.