A set of mono- and dinuclear Au and Ag alkynyl complexes bearing the carba-closo-dodecaboranylethynyl ligand show intense room temperature phosphorescence. The {closo-1-CB} cage participates in an unprecedented way as an electron donating moiety, changing the direction of the charge-transfer excited state.
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http://dx.doi.org/10.1039/c9cc05060d | DOI Listing |
J Phys Chem Lett
December 2024
State Key Laboratory of Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, P. R. China.
Circularly polarized multiple-resonance thermally activated delayed fluorescence (CP-MR-TADF) materials have received widespread attention in recent years, but it remains a formidable challenge to design high-performance CP-MR-TADF emitters concurrently exhibiting high quantum efficiency, narrowband emission, and high dissymmetry factor (). Here, we perform an in-depth theoretical investigation on the CP-MR-TADF materials based on [2.2] paracyclophane (pCp) derivatives.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States.
Designing catalysts with well-defined active sites with chemical functionality responsive to visible light has significant potential for overcoming scaling relations limiting chemical reactions over heterogeneous catalyst surfaces. Visible light can be leveraged to facilitate the removal of strongly bound species from well-defined single cationic sites (Rh) under mild conditions (323 K) when they are incorporated within a photoactive perovskite oxide (Rh-doped SrTiO). CO, a key intermediate in many chemistries, forms stable geminal dicarbonyl Rh complexes (Rh(CO)), that could act as site blockers or poisons during a catalytic cycle.
View Article and Find Full Text PDFJ Comput Chem
January 2025
Department of Mechanical Engineering, Texas Tech University, Lubbock, Texas, USA.
Multi-copper oxidases (MCOs) are enzymes of significant interest in biotechnology due to their efficient catalysis of oxygen reduction to water, making them valuable in sustainable energy production and bio-electrochemical applications. This study employs time-dependent density functional theory (TDDFT) to investigate the electronic structure and spectroscopic properties of the Type 1 (T1) copper site in Azurin, which serves as a model for similar sites in MCOs. Four model complexes of varying complexity were derived from the T1 site, including 3 three-coordinate models and 1 four-coordinate model with axial methionine ligation, to explore the impact of molecular branches and axial coordination.
View Article and Find Full Text PDFJ Chem Phys
December 2024
College of Engineering, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548, Japan and Institute for Molecular Science, 38 Nishigonaka, Myodaiji, Okazaki 444-8585, Japan.
We present a novel theoretical scheme for orbital relaxation in configuration interaction singles (CIS) based on a perturbative treatment of its electronic Hessian, whose analytical derivation is also established in this work. The proposed method, which can be interpreted as a "CIS-then-CIS" scheme, variationally accounts for orbital relaxation in excited states, thus significantly reducing the overestimation of charge-transfer excitation energies commonly associated with standard CIS. In addition, by incorporating de-excitation effects from CIS, we demonstrate that our approach effectively describes single bond dissociation.
View Article and Find Full Text PDFAcc Chem Res
December 2024
Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045, United States.
ConspectusThe surface of a catalyst is crucial for understanding the mechanisms of catalytic reactions at the molecular level and developing new catalysts with higher activity, selectivity, and durability. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) is a technique studying the surface of a sample in the gas phase, mainly identifying chemical identity, analyzing oxidation state, and measuring surface composition.In the last decade, numerous photoelectron spectroscopic methods for fundamental studies of key topics in catalysis using AP-XPS have been developed.
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