Mechanistic investigation of a visible light mediated dehalogenation/cyclisation reaction using iron(iii), iridium(iii) and ruthenium(ii) photosensitizers

被引：34

作者：

Aydogan, Akin ^{[1
]}

Bangle, Rachel E. ^{[2
]}

De Kreijger, Simon ^{[1
]}

Dickenson, John C. ^{[2
]}

Singleton, Michael L. ^{[1
]}

Cauet, Emilie ^{[3
]}

Cadranel, Alejandro ^{[4
,5
,6
]}

Meyer, Gerald J. ^{[2
]}

Elias, Benjamin ^{[1
]}

Sampaio, Renato N. ^{[2
,7
]}

Troian-Gautier, Ludovic ^{[1
]}

机构：

[1] Univ Catholique Louvain UCLouvain, Inst Matiere Condensee & Nanosci IMCN, Mol Chem Mat & Catalysis MOST, Pl Louis Pasteur 1,Bte L4-01-02, B-1348 Louvain La Neuve, Belgium

[2] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA

[3] Univ Libre Bruxelles, Spect Quantum Chem & Atmospher Remote Sensing CP, 50 Av FD Roosevelt, B-1050 Brussels, Belgium

[4] Friedrich Alexander Univ Erlangen Nurnberg, Interdisciplinary Ctr Mol Mat ICMM, Dept Chem & Pharm, Egerlandstr 3, D-91058 Erlangen, Germany

[5] Univ Buenos Aires, Fac Ciencias Exactas & Nat, Dept Quim Inorgan Analit & Quim Fis, Pabellon 2,Ciudad Univ,C1428EHA, Buenos Aires, DF, Argentina

[6] Univ Buenos Aires, CONICET, Inst Quim Fis Mat Medio Ambiente & Energia INQUIM, Pabellon 2,Ciudad Univ,C1128EHA, Buenos Aires, DF, Argentina

[7] Brookhaven Natl Lab, Chem Div, Upton, NY 11973 USA

来源：

CATALYSIS SCIENCE & TECHNOLOGY | 2021年 / 11卷 / 24期

基金：

美国国家科学基金会;

关键词：

EXCITED-STATE PROPERTIES; COMPLEX; PHOTOCHEMISTRY; BENZOPHENONE; PHOTOPHYSICS; NANOSECOND; CATALYSIS; LIGANDS; ALKENES; SYSTEM;

D O I：

10.1039/d1cy01771c

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The mechanism of a visible light-driven dehalogenation/cyclization reaction was investigated using ruthenium(ii), iridium(iii) and iron(iii) photosensitizers by means of steady-state photoluminescence, time-resolved infrared spectroscopy, and nanosecond/femtosecond transient absorption spectroscopy. The nature of the photosensitizer was found to influence the product distribution such that the dehalogenated, non-cyclized products were only detected for the iron photosensitizer. Strikingly, with the iron photosensitizer, large catalytic yields required a low dielectric solvent such as dichloromethane, consistent with a previous publication. This low dielectric solvent allowed ultrafast charge-separation to outcompete geminate charge recombination and improved cage escape efficiency. Further, the identification of reaction mechanisms unique to the iron, ruthenium, and iridium photosensitizer represents progress towards the long-sought goal of utilizing earth-abundant, first-row transition metals for emerging energy and environmental applications.

引用

页码：8037 / 8051

页数：15

共 74 条

[1] Regioselective Aromatic Substitution Reactions of Cyclometalated Ir(III) Complexes: Synthesis and Photochemical Properties of Substituted Ir(III) Complexes That Exhibit Blue, Green, and Red Color Luminescence Emission [J].