Photoactive Metal-to-Ligand Charge Transfer Excited States in 3d⁶ Complexes with Cr⁰, Mn^I, Fe^II, and Co^III

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 4903 - 4920

Published: Feb. 21, 2023

Many coordination complexes and organometallic compounds with the 4d6 5d6 valence electron configurations have outstanding photophysical photochemical properties, which stem from metal-to-ligand charge transfer (MLCT) excited states. This substance class makes extensive use of most precious least abundant metal elements, consequently there has been a long-standing interest in first-row transition photoactive MLCT Semiprecious copper(I) its completely filled 3d subshell is relatively straightforward well explored case, but 3d6 partially d-orbitals lead to energetically low-lying metal-centered (MC) states that can cause undesirably fast state deactivation. Herein, we discuss recent advances made isoelectronic Cr0, MnI, FeII, CoIII compounds, for long-lived become accessible over past five years. Furthermore, possible future developments search new subshells next-generation applications photophysics photochemistry.

Language: Английский

---

Photoinduced Copper-Catalyzed Late-Stage Azidoarylation of Alkenes via Arylthianthrenium Salts

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(25), P. 13542 - 13548

Published: June 12, 2023

The arylethylamine pharmacophore is conserved across a range of biologically active natural products and pharmaceuticals, particularly in molecules that act on the central nervous system. Herein, we present photoinduced copper-catalyzed azidoarylation alkenes at late stage with arylthianthrenium salts, allowing access to highly functionalized acyclic (hetero)arylethylamine scaffolds are otherwise difficult access. A mechanistic study consistent rac-BINAP-CuI-azide (2) as photoactive catalytic species. We show utility new method by expedient synthesis racemic melphalan four steps through C-H functionalization.

Language: Английский

---

Ultrahigh-Strength Textile Fiber-Supported Schiff Base Copper Complexes for Photocatalytic Degradation of Methyl Orange

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: 6(21), P. 13077 - 13088

Published: Oct. 17, 2024

An ultrahigh-strength textile fiber-supported Schiff base copper complex PEEK-SB@Cu(II) was prepared by chloromethylation and amination of a commercially available poly(ether ether ketone) (PEEK) fiber, followed functionalization acetate chelation treatment. The fibers derived from the preparation stages catalytic runs were characterized using diverse techniques to investigate these changes. Moreover, incorporated with NaBH4 presented effective photocatalytic activities for fast exhaustive degradation methyl orange in an aqueous solution rate >99% no more than 2 min. corresponding influencing factors screened confirm that process based on pseudo-first-order reaction kinetic mode, synergistic mechanism proposed interpret process. Furthermore, recyclability stability evaluated over 5 long-term storage at least months, practicability this methodology spinning basket reactor further verified.

Language: Английский

---

The Golden Age of Thermally Activated Delayed Fluorescence Materials: Design and Exploitation

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 12, 2024

Since the seminal report by Adachi and co-workers in 2012, there has been a veritable explosion of interest design thermally activated delayed fluorescence (TADF) compounds, particularly as emitters for organic light-emitting diodes (OLEDs). With rapid advancements innovation materials design, efficiencies TADF OLEDs each primary color points well white devices now rival those state-of-the-art phosphorescent emitters. Beyond electroluminescent devices, compounds have also found increasing utility applications numerous related fields, from photocatalysis, to sensing, imaging beyond. Following our previous review 2017 (

Language: Английский

---

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 6700 - 6902

Published: May 15, 2024

1,10-Phenanthroline (phen) is one of the most popular ligands ever used in coordination chemistry due to its strong affinity for a wide range metals with various oxidation states. Its polyaromatic structure provides robustness and rigidity, leading intriguing features numerous fields (luminescent scaffolds, catalysis, supramolecular chemistry, sensors, theranostics, etc.). Importantly, phen offers eight distinct positions functional groups be attached, showcasing remarkable versatility such simple ligand. As result, has become landmark molecule chemists, serving as must-use ligand versatile platform designing polyfunctional arrays. The extensive use substituted phenanthroline different metal ions resulted diverse array complexes tailored applications. For instance, these have been utilized sensitizers dye-sensitized solar cells, luminescent probes modified antibodies biomaterials, creation elegant architectures like rotaxanes catenanes, exemplified by Sauvage's Nobel Prize-winning work 2016. In summary, found applications almost every facet chemistry. An aspect specific reactivity each pair carbon atoms ([2,9], [3,8], [4,7], [5,6]), enabling functionalization Furthermore, it possible differentiate position pairs, resulting non-symmetrical systems tremendous versatility. this Review, authors aim compile categorize existing synthetic strategies stepwise polyfunctionalization positions. This comprehensive toolbox will aid chemists virtually any survey encompass seminal from 1950s present day. scope Review limited 1,10-phenanthroline, excluding more intracyclic heteroatoms or fused aromatic cycles. Overall, primary goal highlight both old recent that find applicability mentioned By doing so, hope establish first reference synthesis, covering all on backbone, inspire concerned devise new not yet explored.

Language: Английский

---

Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Language: Английский

---

Examining the impact of hydroxy group position on antibacterial activity of copper complexes derived from vanillin-based Schiff bases: Experimental and computational analysis

Chemosphere, Journal Year: 2025, Volume and Issue: 371, P. 144063 - 144063

Published: Jan. 6, 2025

Language: Английский

---

Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Language: Английский

---

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

---

The Nephelauxetic Effect Becomes an Important Design Factor for Photoactive First‐Row Transition Metal Complexes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 14, 2023

Abstract The expansion of d‐orbitals as a result metal‐ligand bond covalence, the so‐called nephelauxetic effect, is well‐established concept coordination chemistry, yet its importance for design new photoactive complexes based on first‐row transition metals only beginning to be recognized. Until recently, much focus has been optimizing ligand field strength, geometries, and molecular rigidity, but now it becomes evident that effect can game changer regarding photophysical properties 3d metal in solution at room temperature. In Cr III Mn IV with d 3 valence electron configuration, was exploited shift well‐known ruby‐like red luminescence near‐infrared spectral region. Fe II Co low‐spin 6 charge‐transfer excited states were stabilized respect detrimental metal‐centered states, improve their enhance application potential. isoelectronic (3d ) isocyanide 0 I , likely play well, enabling other favorable photoreactivity. This minireview illustrates broad applicability tailoring photochemical compounds made from abundant metals.

Language: Английский

---