Making Mo(0) a Competitive Alternative to Ir(III) in Phosphors and Photocatalysts

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Iridium is used in commercial light-emitting devices and photocatalysis but among the rarest stable chemical elements. Therefore, replacing iridium(III) photoactive molecular complexes with abundant metals of great interest. First-row transition generally tend to yield poorer luminescence behavior, it remains difficult obtain excited states redox properties that exceed those noble-metal-based photocatalysts. Here, we overcome these challenges a nonprecious second-row metal. Tailored coordination spheres for molybdenum(0) lead photoluminescence quantum yields rival photochemical reduction reactions not normally achievable become possible. These developments open new perspectives noble lighting applications Earth-abundant advancing metal-based beyond current limits.

Language: Английский

A Blessing and a Curse: Remote Ligand Functionalization Modulates ³MLCT Relaxation in Group 6 Tricarbonyl Complexes

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

We recently reported a molecular design for carbonylpyridine molybdenum(0) complexes that unlocks long-lived luminescent and photoactive charge-transfer states. Here, we translate this strategy to chromium(0), tungsten(0) report three fully characterized tricarbonyl metal(0) featuring tripodal ligand with remote n-butyl substituent in the backbone. All show phosphorescence red near-infrared spectral region from metal-to-ligand excited Surprisingly, alkyl chain significantly affects state relaxation: lifetimes are shortened solution but extended solid by one order of magnitude compared complex methyl substituent. Temperature-dependent luminescence NMR spectroscopy combination quantum chemical calculations reveal reasons these disparate effects. The distorts metal coordination geometry. resulting structural flexibility flattens potential energy surfaces solution, which lowers barrier population distorted metal-centered states facilitates nonradiative relaxation. In state, rigidified separates neighboring molecules, reduces self-quenching. Our study sheds light on relationship between structure relaxation inform development based earth-abundant metals.

Language: Английский

Trendbericht Photochemie 2025

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(4), P. 56 - 67

Published: March 31, 2025

Abstract Dieser Trendbericht erläutert Erkenntnisse der letzten beiden Jahre aus Sicht von Wissenschaftlerinnen und Wissenschaftlern des interdisziplinären, durch die DFG geförderten Konsortiums Transregio 325. Die Autorinnen Autoren forschen vor allem zu chemischer Photokatalyse beleuchten besonders Themen mit molekülchemischer Komponente.