Manipulation of Charge-Transfer States by Molecular Design: Perspective from “Dynamic Exciton” DOI
Hiroshi Imahori, Yasuhiro Kobori, Hironori Kaji

et al.

Accounts of Materials Research, Journal Year: 2021, Volume and Issue: 2(7), P. 501 - 514

Published: June 29, 2021

Conspectus"Dynamic exciton", an umbrella term concept in photochemistry, plays important role nature, science, and technology, especially photoinduced electrically induced electron transfer (ET) between a donor (D) acceptor (A). Typically, exciton molecular D–A systems is considered locally excited (LE) state of (D*) or (A*) molecule, but let us extend the terminology "exciton" to integrated class LE, charge-transfer (CT), charge-separated (CS) states. The degree CT (0–100%), spin multiplicity, interaction (i.e., electronic coupling) are pivotal factors "exciton". Another aspect strongly related "dynamic" by movement atomic nuclei vibration, rotation, fluctuation) their collective motions controlling behaviors electrons spins passage time. "dynamic exciton" should cover wide variety photochemical phenomena that all essential for energy conversion devices processes including various kinds living systems. In these, huge amount nuclear motional modes may cooperatively be entangled orbitals. Thus, idea behind includes usage cooperation spin–orbital, as electron–phonon coupling innovative designs materials assemblies. For this, it particularly examine how this roles on couplings, intermediate geometries mobilities, energies, characters, so on. We draw researchers' attention vibronic effect, like entropy side chains conjugated polymer modulate time-dependently at charge delocalization dissociation, which reinforced three-dimensionally D/A domain interface organic photovoltaics (OPVs). addition, realize ultimate high-performance OPVs, voltage loss must diminished; i.e., difference band gap open circuit caused part interfacial recombination via vibrational relaxation. Attaining efficient excited-state migration with prevention relaxation would possibly overcome issues primary event, when we understand low-frequency disorder movements phonon solid state. Importantly, state-to-CS OPVs opposite process CS state-to-excited light-emitting diodes (OLEDs). Specifically, intramolecular linked intermolecular hold prominent position both OLEDs, intrinsic similarity seen mutual interplay among CT, states such facilitated dynamic effects. These facts encourage work manipulation logical design, achieving OLEDs. Along some examples here introduce comprehensive, photochemistry systems, eventually making innovations electronics, energy, medicine/health care, functional materials.

Language: Английский

A review of enantioselective dual transition metal/photoredox catalysis DOI
Hong‐Hao Zhang, Hui Chen, Chengjian Zhu

et al.

Science China Chemistry, Journal Year: 2020, Volume and Issue: 63(5), P. 637 - 647

Published: April 1, 2020

Language: Английский

Citations

150
Recent advances in transition-metal-catalysed asymmetric coupling reactions with light intervention DOI

Fu‐Dong Lu,

Jun Chen, Xuan‐Feng Jiang

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(22), P. 12808 - 12827

Published: Jan. 1, 2021

Transition metal-catalysed asymmetric coupling has been established as a robust tool for constructing complex organic molecules. Although this area extensively studied, the development of efficient protocols to construct stereogenic centres with excellent regio- and enantioselectivities is highly desirable remains challenging. Asymmetric transition metal catalysis light intervention provides practical alternative strategy current methods considerably expands synthetic utility result abundant feedstocks mild conditions. This tutorial review comprehensively summarizes recent advances in transition-metal-catalysed reactions intervention; particular, concise analysis substrate scope mechanistic scenarios governing stereocontrol discussed.

Language: Английский

Citations

141
Visible Light Assisted Radical‐Polar/Polar‐Radical Crossover Reactions in Organic Synthesis DOI
Shivani Sharma, Jitender Singh, Anuj Sharma

et al.

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(13), P. 3146 - 3169

Published: April 10, 2021

Abstract Chemists are generally familiar with polar reactions and radical reactions, in comparison, underdeveloped. In the last few years, however, novel concept of amalgamation above two form radical‐polar crossover (RPCO) polar‐radical (PRCO) has emerged as a valuable powerful tool. This methodology tends to bridge gap between well overcomes limitations both traditional chemistry. By bringing together unorthodox chemistry radicals orthodox carbocations carbanions, green quotient such is significantly improved. The development shaping up this area years synthetically important transformations summarised review. magnified image

Language: Английский

Citations

124
Photocatalytic three-component asymmetric sulfonylation via direct C(sp3)-H functionalization DOI
Shi Cao, Wei Hong, Ziqi Ye

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: April 22, 2021

Language: Английский

Citations

121
Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates DOI Creative Commons
Chi Zhang, Zhong‐Liang Li, Qiang‐Shuai Gu

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Jan. 20, 2021

Abstract Recently, with the boosted development of radical chemistry, enantioselective functionalization C( sp 3 )–H bonds via a pathway has witnessed renaissance. In principle, two distinct catalytic modes, distinguished by steps in which stereochemistry is determined (the formation step or step), can be devised. This Perspective discusses state-of-the-art area involving intermediates as well future challenges and opportunities.

Language: Английский

Citations

116
Metallaphotoredox catalysis for sp3C–H functionalizations through hydrogen atom transfer (HAT) DOI
Jingchang Zhang, Magnus Rueping

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(12), P. 4099 - 4120

Published: Jan. 1, 2023

sp 3 C–H functionalizations under the combination of photocatalytic HAT and transition metal catalysis.

Language: Английский

Citations

89
Light-empowered contra-thermodynamic stereochemical editing DOI

Peng‐Zi Wang,

Wen‐Jing Xiao, Jia‐Rong Chen

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 7(1), P. 35 - 50

Published: Nov. 16, 2022

Language: Английский

Citations

77
Photocatalyzed Enantioselective Functionalization of C(sp3)–H Bonds DOI
Guo‐Qiang Xu, Wei David Wang, Peng‐Fei Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1209 - 1223

Published: Jan. 3, 2024

Owing to its diverse activation processes including single-electron transfer (SET) and hydrogen-atom (HAT), visible-light photocatalysis has emerged as a sustainable efficient platform for organic synthesis. These provide powerful avenue the direct functionalization of C(sp3)–H bonds under mild conditions. Over past decade, there have been remarkable advances in enantioselective bond via combined with conventional asymmetric catalysis. Herein, we summarize involving discuss two main pathways this emerging field: (a) SET-driven carbocation intermediates are followed by stereospecific nucleophile attacks; (b) photodriven alkyl radical further enantioselectively captured (i) chiral π-SOMOphile reagents, (ii) stereoselective transition-metal complexes, (iii) another distinct stereoscopic species. We aim key reaction design, catalyst development, mechanistic understanding, new insights into rapidly evolving area research.

Language: Английский

Citations

36
Photoredox/Cr-catalyzed enantioselective radical-polar crossover transformation via C-H functionalization DOI Creative Commons
Siyuan Tang,

Z. Z. Wang,

Ao Yu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 4, 2025

Asymmetric multicomponent reactions that aim to control multiple chiral centers with high selectivity in a single step remain an on-gonging challenge. The realm of enantioselective radical-polar crossover transformation achieved through C-H Functionalization has yet be fully explored. Herein, we present successful description photoredox/Cr-catalyzed three-component (hetero)arylalkylation 1,3-dienes functionalization. A diverse array homoallylic alcohols could obtained good excellent yields, accompanied by outstanding enantioselectivity. asymmetric build two simultaneously and demonstrates broad substrate tolerance, accommodating various drug-derived aldehydes, (hetero)aromatics, 1,3-diene derivatives. Preliminary mechanistic studies indicate the involvement radical intermediate, allylic chromium species reacting aliphatic aromatic aldehydes Zimmerman–Traxler transition states enabled dual photoredox catalysis. ongoing Here, authors photoredox- chromium-catalyzed

Language: Английский

Citations

2
Catalytic Allylation of Aldehydes Using Unactivated Alkenes DOI

Shun Tanabe,

Harunobu Mitsunuma, Motomu Kanai

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(28), P. 12374 - 12381

Published: July 1, 2020

Simple feedstock organic molecules, especially alkenes, are attractive starting materials in synthesis because of their wide availability. Direct utilization such bulk, inert molecules for practical and selective chemical reactions, however, remains limited. Herein, we developed a ternary hybrid catalyst system comprising photoredox catalyst, hydrogen-atom-transfer chromium complex enabling catalytic allylation aldehydes with simple including lower alkenes. The reaction proceeded under visible-light irradiation at room temperature high functional group tolerance. was extended to an asymmetric variant by employing chiral catalyst.

Language: Английский

Citations

135