Living Long and Prosperous: Productive Intraligand Charge-Transfer States from a Rhenium(I) Terpyridine Photosensitizer with Enhanced Light Absorption

The ground- and excited-state properties of six rhenium(I) κ2N-tricarbonyl complexes with 4′-(4-substituted-phenyl)terpyridine ligands bearing substituents of different electron-donating abilities were evaluated. Significant modulation of the electrochemical potentials and a nearly 4-fold variation of the triplet metal-to-ligand charge-transfer (3MLCT) lifetimes were observed upon going from CN to OMe. With the more electron-donating NMe2 group, we observed in the κ2N complex the appearance of a very strong absorption band, red-shifted by ca. 100 nm with respect to the other complexes. This was accompanied by a dramatic enhancement of the excited-state lifetime (380 vs 1.5 ns), and a character change from 3MLCT to intraligand charge transfer (3ILCT), despite the remote location of the substituent. The dynamics and character of the excited states of all complexes were assigned by combining transient IR spectroscopy, IR spectroelectrochemistry, and (time-dependent) density functional theory calculations. Selected complexes were evaluated as photosensitizers for hydrogen production, with the κ2N-NMe2 complex resulting in a stable and efficient photocatalytic system reaching TONRe values of over 2100, representing the first application of the 3ILCT state of a rhenium(I) carbonyl complex in a stable photocatalytic system

Vibrational Couplings in Hydridocarbonyl Complexes: A 2D-IR Perspective

Hydridocarbonyl complexes, a class of industrially relevant catalysts, contain both the M–H and M–CO moieties. Here, using two-dimensional infrared spectroscopy, we examine the coupling of the typically weak M–H stretching mode and the intense M(C≡O) mode. By studying a series of Ir(I)- and Ir(III)-based hydridocarbonyl complexes, we show that the arrangement of the H and CO ligands in a trans configuration leads to strong vibrational coupling and mode delocalization. In contrast, a cis arrangement leads to no coupling, with the localized M–H mode having a much larger anharmonicity. These results highlight a promising strategy for enhancing the M–H vibration by intensity borrowing from the strong C≡O modes in a trans configuration, allowing for direct determination by infrared spectroscopy of both the oxidation (by frequency shifts) and the protonation state (via vibrational coupling) of the complex, in mechanistic studies of proton-coupled electron transfer reactions

Nanosecond protein dynamics in a red/green cyanobacteriochrome revealed by transient IR spectroscopy

Over the last decades, photoreceptive proteins were extensively studied with biophysical methods to gain a fundamental understanding of their working mechanisms and further guide the development of optogenetic tools. Time-resolved infrared (IR) spectroscopy is one of the key methods to access their functional non-equilibrium processes with high temporal resolution but has the major drawback that experimental data are usually highly complex. Linking the spectral response to specific molecular events is a major obstacle. Here, we investigate a cyanobacteriochrome photoreceptor with a combined approach of transient absorption spectroscopy in the visible and IR spectral regions. We obtain kinetic information in both spectral regions by analysis with two different fitting methods: global multiexponential fitting and lifetime analysis. We investigate the ground state dynamics that follow photoexcitation in both directions of the bi-stable photocycle (Pr* and Pg*) in the nanosecond and microsecond time regimes. We find two ground state intermediates associated with the decay of Pr* and four with Pg* and report the macroscopic time constants of their interconversions. One of these processes is assigned to a structural change in the protein backbone

Shedding Light on the Molecular Surface Assembly at the Nanoscale Level: Dynamics of a Re(I) Carbonyl Photosensitizer with a Coadsorbed Cobalt Tetrapyridyl Water Reduction Catalyst on ZrO2

We present systematic kinetic studies of the interaction of a rhenium-based photosensitizer with a cobalt(II) tetrapyridyl water reduction catalyst coadsorbed on ZrO2 by transient IR and visible spectroscopies. The study focuses on the competition between the reduction of the excited photosensitizer by an electron donor in solution and nonproductive quenching between the photosensitizer and the catalyst, either by Dexter energy transfer or by electron transfer followed by ultrafast geminate recombination. The implications of both interactions for the charge transfer reactions on the surface are investigated. We find that the kinetics of the system as a whole and the achievable yield of reduced photosensitizer are determined by the inhomogeneous distribution of next neighbor distances between photosensitizers and the water reduction catalysts at the nanoscale level. This provides insight for rational design of heterogeneous water splitting systems with coimmobilized photosensitizers and catalysts

Dynamic dimer–monomer equilibrium in a cycloruthenated complex of [Re(η6-C6H6)2]+

Cycloruthenation is a well known process in organometallic ruthenium chemistry. In this work, we report unprecedented cycloruthenated rhenium bis-arene compounds with planar chirality. In a two-step process, the reaction of acetyl-pyridine with [Re(η6-C6H6)2]+ introduced a pyridinyl-methanol ligand at one of the arene rings. Coordination of [Ru(CO)2Cl2] led to cycloruthenation, and the products were obtained as two diastereomeric pairs of enantiomers. Under basic pH conditions, the two pairs of enantiomers undergo spontaneous and reversible dimerization. The cycloruthenated monomers were fully characterized, and the dimerization process was studied by NMR, IR spectroscopy, and DFT calculations

Dye‐Sensitized Photocatalysis: Hydrogen Evolution and Alcohol‐to‐Aldehyde Oxidation without Sacrifical Electron Donor

There is a growing interest in developing dye‐sensitized photocatalytic systems (DSPs) to produce molecular hydrogen (H 2 ) as alternative energy source. To improve the sustainability of this technology, we replaced the sacrificial electron donor (SED), typically an expensive and polluting chemical, with an alcohol oxidation catalyst. This study demonstrates the first dye‐sensitized system using a diketopyrrolopyrrole dye covalently linked to 2,2,6,6‐tetramethyl‐1‐piperidine‐ N ‐oxyl (TEMPO) based catalyst for simultaneous H 2 evolution and alcohol‐to‐aldehyde transformation operating in water with visible irradiation.</p

Paisaje Cultural Urbano e Identitad Territorial

Linguaggio contemporaneo e preesistenze: dialogo in un mondo globalizzato Il tema del rapporto con l’antico trova una giusta dimensione operativa quando, superando la sfera delle ideologie e quella delle opposte ragioni della memoria e dello sviluppo, indirizza positivamente l’azione progettuale ora per differenza ora per empatia, a seconda delle circostanze, ma crea sempre una forte tensione tra le ragioni dell’esistente e le necessità del nuovo. Intervenire nell’antico e per l’antico significa, pertanto, riprogettare il nostro modo di relazionarci con il passato, rinegoziandone identità e valori alla luce del nostro presente. Da questa angolazione il patrimonio non è solo lo spazio della memoria o quello della storia, ma diviene lo spazio del desiderio che trae alimento dal mito dell’araba fenice: esso, come principio evolutivo, rappresenta l’inizio di un incessante ricominciamento e l'occasione per una mediazione tra globale e locale