Search results for "Photochemistry | Reviews Showcase"

Developments in the dehydrogenative electrochemical synthesis of 3,3′,5,5′-tetramethyl-2,2′-biphenol

2021

Abstract The symmetric biphenol 3,3′,5,5′‐tetramethyl‐2,2′‐biphenol is a well‐known ligand building block and is used in transition‐metal catalysis. In the literature, there are several synthetic routes for the preparation of this exceptional molecule. Herein, the focus is on the sustainable electrochemical synthesis of 3,3′,5,5′‐tetramethyl‐2,2′‐biphenol. A brief overview of the developmental history of this inconspicuous molecule, which is of great interest for technical applications, but has many challenges for its synthesis, is provided. The electro‐organic method is a powerful, sustainable, and efficient alternative to conventional synthesis to obtain this symmetric biphenol up to the …

Strain Release Chemistry of Photogenerated Small‐Ring Intermediates

2021

Abstract Photochemical processes, such as isomerizations and cycloadditions, have proven to be very useful in the construction of highly strained molecular frameworks. Photoinduced ring strain enables subsequent exergonic reactions which do not require the input of additional chemical energy and provides a variety of attractive synthetic options leading to complex structures. This review covers the progress achieved in the application of sequences combining excitation by ultraviolet light to form strained intermediates, which are further transformed to lower energy products in strain‐release reactions. As ring strain is considerable in small ring systems, photogenerated three‐ and four‐memb…

A theoretical insight into the photophysics of psoralen

2006

Psoralen photophysics has been studied on quantum chemistry grounds using the multiconfigurational second-order perturbation method CASPT2. Absorption and emission spectra of the system have been rationalized by computing the energies and properties of the low-lying singlet and triplet excited states. The S1 ππ* state has been determined to be responsible of the lowest absorption and fluorescence bands and to initially carry the population in the photophysical processes related to the phototherapeutic properties of psoralen derivatives. The low-lying T1 ππ* state is, on the other hand, protagonist of the phosphorescence, and its prevalent role in the reactivity of psoralen is suggested to b…

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

2019

Abstract Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN6] chromophore [Cr(tpe)2]3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)2]3+ are redox non‐innocent, …

Unexpected photochemistry and charge-transfer complexes of [CB11H12]2 carborane

2008

Although the [CB11H12]¯carborane does not exhibit an absorption band inUV, its triplet excited state can be generated upon 308 nm laser excitation; also unexpectedly carborane acts as electron donor forming a charge transfer complex with methylviologen that upon illumination gives rise to viologen radical cation. Galletero Pedroche, M.Sales, Sales.Galletero@uv.es

Visible Light Photocatalysis by a Titania-Rhodium (III) Complex

2009

Controlling Spin-Correlated Radical Pairs with Donor-Acceptor Dyads: A New Concept to Generate Reduced Metal Complexes for More Efficient Photocataly…

2021

Abstract One‐electron reduced metal complexes derived from photoactive ruthenium or iridium complexes are important intermediates for substrate activation steps in photoredox catalysis and for the photocatalytic generation of solar fuels. However, owing to the heavy atom effect, direct photochemical pathways to these key intermediates suffer from intrinsic efficiency problems resulting from rapid geminate recombination of radical pairs within the so‐called solvent cage. In this study, we prepared and investigated molecular dyads capable of producing reduced metal complexes via an indirect pathway relying on a sequence of energy and electron transfer processes between a Ru complex and a cova…

Green-Light Activation of Push-Pull Ruthenium(II) Complexes.

2020

Abstract Synthesis, characterization, electrochemistry, and photophysics of homo‐ and heteroleptic ruthenium(II) complexes [Ru(cpmp)2]2+ (22+) and [Ru(cpmp)(ddpd)]2+ (32+) bearing the tridentate ligands 6,2’’‐carboxypyridyl‐2,2’‐methylamine‐pyridyl‐pyridine (cpmp) and N,N’‐dimethyl‐N,N’‐dipyridin‐2‐ylpyridine‐2,6‐diamine (ddpd) are reported. The complexes possess one (32+) or two (22+) electron‐deficient dipyridyl ketone fragments as electron‐accepting sites enabling intraligand charge transfer (ILCT), ligand‐to‐ligand charge transfer (LL'CT) and low‐energy metal‐to‐ligand charge transfer (MLCT) absorptions. The latter peak around 544 nm (green light). Complex 22+ shows 3MLCT phosphorescenc…

Applications of Quantum Chemistry in Spectroscopy: Molecules, Complexes of Van der Waals, trapped Molecules

2009

I described in this memory my activities as a researcher at Tomsk well before 2003, in succession to the State University of Tomsk in the Faculty of Physics, Institute of Physics of Siberia, and the Institute of 'Atmospheric Optics, in France since then, mostly at the University of Bourgogne (ICB), but also at the University of Lille I (PhLAM) and the University of Marne-la-Vallée (LCT). Part of my work has been dedicated to the evaluation by calculating ab initio of rovibrational constants for quasi-spherical molecules. The centrifugal distortion constants and the dipole moment of the molecule SO2F2 were calculated to validate the tensor theory and interpreter the spectrum. I twas shown th…

Structural Motifs of Alkali Metal Superbases in Non‐coordinating Solvents

2020

Abstract Lochmann–Schlosser superbases (LSB) are a standard reagent in synthetic chemistry to achieve an exchange of a proton on an organic framework with an alkali metal cation, which in turn can be replaced by a wide range of electrophilic groups. In standard examples, the deprotonating reagent consists of an equimolar mixture of n‐butyllithium and potassium t‐butoxide. However, the nature of the reactive species could not be pinned down either for this composition or for similar mixtures with comparable high reactivity. Despite the poor solubility and the fierce reactivity, some insights into this mixture were achieved by some indirect results, comparison with chemically related systems,…