Redox Chemistry of Benzimidazoline (BIH) and Benzimidazolium (BI<sup>+</sup>)-Initiation, Exploration and Expansion- DOI
Eietsu Hasegawa, Shin‐ya Takizawa

Journal of Synthetic Organic Chemistry Japan, Journal Year: 2024, Volume and Issue: 82(10), P. 1001 - 1018

Published: Oct. 1, 2024

Reduction and oxidation (redox) reactions are fundamental chemical processes frequently involve single electron transfer (SET). Nicotinamide adenine dinucleotide is an eminent redox coenzyme, the oxidized form (NAD+) converted to reduced (NADH) for its use in biological processes. Benzimidazoline (BIH) benzimidazolium (BI+) recognized as artificial analogues of NADH NAD+. Redox chemistry BIH has started mid 80s which 1,3-dimethyl-2-phenylbenzimidazoline (BIH-Ph) was used a hydride donor. Subsequently, hydrogen atom donating property BIH-Ph explored. Following thermodynamic well kinetic investigations 2-substituted-1,3-dimethylbenzimidazolines (BIH-R) revealed that SET from BIH-R produces their radical cations (BIH-R•+) release give forms (BI+-R). Deprotonation BIH-R•+ by appropriate bases radicals BI•-R act strong donors. We began investigate photoinduced (PET) 90s. Breakthroughs were made areas photocatalytic CO2 reduction n-type doping organic semiconductors around 15 years ago. Thus far, have been utilized various applications such reduction, photoredox catalysis, photosynthesis, O2 semiconductor devices. BI+-R much less explored than recently begun. In this review article, we described brief history representative BIH-R. addition, recent studies catalysts presented.

Language: Английский

Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocyanides DOI
Dooyoung Kim, Michael C. Rosko, Felix N. Castellano

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19193 - 19204

Published: July 2, 2024

There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention this field, and most cases, sterically driven approaches are used optimize their lifetimes. This study presents a series of three-coordinate copper(I) (Cu1–Cu3) where the lifetime is extended by triplet–triplet energy transfer. The heteroleptic compounds feature cyclohexyl-substituted β-diketiminate (CyNacNacMe) paired with aryl isocyanide ligands, giving general formula Cu(CyNacNacMe)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl for Cu1; CN-pyr 1-pyrenyl Cu2; CN-dmp-pyr 2,6-dimethyl-4-(1-pyrenyl)phenyl Cu3). nature, energies, dynamics low-energy triplet excited states assessed combination photoluminescence measurements at room temperature 77 K, ultrafast transient absorption (UFTA) spectroscopy, DFT calculations. pyrene-decorated isocyanides (Cu2 Cu3) exhibit resulting from transfer (TTET) between short-lived charge-transfer state (3CT) long-lived pyrene-centered (3pyr). TTET process irreversible Cu3, producing exclusively 3pyr state, Cu2, 3CT nearly isoenergetic, enabling reversible luminescence. improved photophysical properties Cu2 Cu3 result improvements activity both photocatalytic stilbene E/Z isomerization via photoredox transformations involving hydrodebromination C–O bond activation. These results illustrate that achieved through newly conceived photosynthetically relevant metal complexes.

Language: Английский

Citations

7
Throwing Light on Synthetic Molecular Photoelectrocatalysis (Part II): selected recent transformations of organic compounds and a future perspective in organic synthesis DOI Creative Commons
Erick Steven Patiño-Alonzo, José Manuel Ramos-Villaseñor, Julio Romero‐Ibañez

et al.

Current Opinion in Electrochemistry, Journal Year: 2025, Volume and Issue: unknown, P. 101674 - 101674

Published: Feb. 1, 2025

Language: Английский

Citations

0
Sterically Encumbered Aryl Isocyanides Extend Excited-State Lifetimes and Improve the Photocatalytic Performance of Three-Coordinate Copper(I) β-Diketiminate Charge-Transfer Chromophores DOI
Dooyoung Kim, Thomas S. Teets

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16848 - 16855

Published: June 10, 2024

Copper(I) complexes are prominent candidates to replace noble metal-based photosensitizers. We recently introduced a three-coordinate design for copper(I) charge-transfer chromophores that pair β-diketiminate ligands with aryl isocyanides. The excited-state lifetime in these compounds can be extended using bichromophoric "triplet reservoir" strategy, which comes at the expense of decrease energy and reducing power. In this work, we introduce complementary, sterically driven strategy increasing lifetimes photosensitizers, gives higher-energy, more strongly triplet state than does bichromophore approach. presented (Cu1–Cu4) have general formula Cu(CyNacNacMe)(CN-Ar), where CyNacNacMe is cyclohexyl-substituted CN-Ar an isocyanide variable steric profile. Their structural features electrochemical photophysical properties described. encumbered 2,6-diisopropylphenyl or m-terphenyl (Cu2–Cu4) exhibit prolonged relative those parent 2,6-dimethylphenyl compound Cu1. Specifically, one compounds, Cu3, displays 276 ns, approximately 30 times longer Cu1 (9.3 ns). photoluminescence quantum yield Cu3 (0.09) also increases by two orders magnitude compared (0.0008). strong power (*Eox = −2.4 V vs Fc+/0) long lead higher yields photoredox photocatalytic isomerization reactions, include dehalogenation and/or hydrodgenation benzophenone substrates, C–O bond activation lignin model substrate, E/Z stilbene.

Language: Английский

Citations

3
Long Excited-State Lifetimes in Three-Coordinate Copper(I) Com-plexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocy-anides DOI Creative Commons
Dooyoung Kim, Michael C. Rosko, Felix N. Castellano

et al.

Published: March 26, 2024

There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention this field, and most cases, sterically-driven approaches are used optimize their lifetimes. This study presents a series of three-coordinate copper(I) (Cu1–Cu3) where the lifetime is extended by triplet-triplet energy transfer. The heteroleptic compounds feature cyclohexyl-substituted β-diketiminate (CyNacNacMe) paired with aryl isocyanide ligands, giv-ing general formula Cu(CyNacNacMe)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl for Cu1; CN-pyr 1-pyrenyl Cu2; CN-dmp-pyr 2,6-dimethyl-4-(1-pyrenyl)phenyl Cu3). nature, energies, dynamics low-energy triplet excited states assessed combination photoluminescence measurements at room temperature 77 K, ultrafast transient absorp-tion (UFTA) spectroscopy, DFT calculations. featuring pyrene-decorated isocyanides (Cu2 Cu3) exhibit resulting from triplet–triplet transfer (TTET) between short-lived charge-transfer state (3CT) long-lived pyrene-centered (3pyr). TTET process irreversible Cu3, producing exclusively 3pyr state, Cu2 3CT nearly isoenergetic, enabling reversible luminescence. improved photophysical proper-ties Cu3 result photocatalytic activity stilbene E/Z isomerization via photoredox reactivity trans-formations involving hydrodebromination C–O bond activation. These results illustrate that achieved through resulted newly conceived photosynthetically-relevant metal complexes.

Language: Английский

Citations

2
Redox Chemistry of Benzimidazoline (BIH) and Benzimidazolium (BI<sup>+</sup>)-Initiation, Exploration and Expansion- DOI
Eietsu Hasegawa, Shin‐ya Takizawa

Journal of Synthetic Organic Chemistry Japan, Journal Year: 2024, Volume and Issue: 82(10), P. 1001 - 1018

Published: Oct. 1, 2024

Reduction and oxidation (redox) reactions are fundamental chemical processes frequently involve single electron transfer (SET). Nicotinamide adenine dinucleotide is an eminent redox coenzyme, the oxidized form (NAD+) converted to reduced (NADH) for its use in biological processes. Benzimidazoline (BIH) benzimidazolium (BI+) recognized as artificial analogues of NADH NAD+. Redox chemistry BIH has started mid 80s which 1,3-dimethyl-2-phenylbenzimidazoline (BIH-Ph) was used a hydride donor. Subsequently, hydrogen atom donating property BIH-Ph explored. Following thermodynamic well kinetic investigations 2-substituted-1,3-dimethylbenzimidazolines (BIH-R) revealed that SET from BIH-R produces their radical cations (BIH-R•+) release give forms (BI+-R). Deprotonation BIH-R•+ by appropriate bases radicals BI•-R act strong donors. We began investigate photoinduced (PET) 90s. Breakthroughs were made areas photocatalytic CO2 reduction n-type doping organic semiconductors around 15 years ago. Thus far, have been utilized various applications such reduction, photoredox catalysis, photosynthesis, O2 semiconductor devices. BI+-R much less explored than recently begun. In this review article, we described brief history representative BIH-R. addition, recent studies catalysts presented.

Language: Английский

Citations

0