Synthesis and characterisation of homoleptic 2,9-diaryl-1,10-phenanthroline copper(<scp>i</scp>) complexes: influencing selectivity in photoredox-catalysed atom-transfer radical addition reactions

Nicholls, Thomas P.; Caporale, Chiara; Massi, Massimiliano; Gardiner, Michael G.; Bissember, Alex C.

doi:10.1039/c8dt04116d

Cited by 27 publications

(23 citation statements)

References 72 publications

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“…Our study complements ongoing research on photoactive complexes with other Earth-abundant metal elements such as Fe, − Cu, − Cr, − Co, Ni, − Zr, , W, ,,− and Ce, as well as current research on new metal-free organic photosensitizers. − …”

Section: Introductionsupporting

confidence: 64%

“…Our study complements ongoing research on photoactive complexes with other Earth-abundant metal elements such as Fe, [9][10][11][12][13][14][15] Cu, [40][41][42][43][44][45][46][47][48][49][50] Cr, [51][52][53][54] Co, 55 Ni, [56][57][58] Zr, [59][60] W, [34][35][61][62][63] and Ce, 64 as well as current research on new metal-free organic photosensitizers. [65][66][67][68][69]…”

Section: Long-lived Strongly Emissive and Highly Reducing Excited Stsupporting

confidence: 55%

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Long-Lived, Strongly Emissive, and Highly Reducing Excited States in Mo(0) Complexes with Chelating Isocyanides

et al. 2019

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Newly discovered tris(diisocyanide)molybdenum(0) complexes are Earth-abundant isoelectronic analogs of the well-known class of [Ru(-diimine) 3 ] 2+ compounds with long-lived 3 MLCT (metal-to-ligand charge transfer) excited states that lead to rich photophysics and photochemistry. Depending on ligand design, luminescence quantum yields up to 0.20 and microsecond excited state lifetimes are achieved in solution at room temperature, both significantly better than for [Ru(2,2'-bipyridine) 3 ] 2+. The excited Mo(0) complexes can induce chemical reactions that are thermodynamically too demanding for common precious metal based photosensitizers, including the widely employed fac-[Ir(2-phenylpyridine) 3 ] complex, as demonstrated on a series of light-driven aryl-aryl coupling reactions. The most robust Mo(0) complex exhibits stable photoluminescence and remains photoactive after continuous irradiation exceeding two months. Our comprehensive optical spectroscopic and photochemical study shows that Mo(0) complexes with diisocyanide chelate ligands constitute a new family of luminophores and photosensitizers, which is complementary to precious metal based 4d 6 and 5d 6 complexes and represents an alternative to non-emissive Fe(II) compounds. This is relevant in the greater context of sustainable photophysics and photochemistry, as well as for possible applications in lighting, sensing, and catalysis.

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Section: Introductionsupporting

confidence: 64%

Section: Long-lived Strongly Emissive and Highly Reducing Excited Stsupporting

confidence: 55%

Long-Lived, Strongly Emissive, and Highly Reducing Excited States in Mo(0) Complexes with Chelating Isocyanides

et al. 2019

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“…This steric demand impedes the reorientation from the tetrahedral Cu(I) to the square planar Cu(II) coordination environment in the course of the oxidation and therefore shifts the oxidation potentials to more positive values. For all described complexes, the oxidation potentials are considerably lower than those of homoleptic diimine complexes, such as [Cu(I)(phenanthroline) 2 ] + complexes with anodic potentials of 0.1 to 0.8 V [21,53–55] . Also, the related heteroleptic [Cu(I)(xantphos)(4 H ‐imidazolato)] complexes show considerably higher oxidation potentials (ca.…”

Section: Resultsmentioning

confidence: 90%

Ligand‐Induced Donor State Destabilisation – A New Route to Panchromatically Absorbing Cu(I) Complexes

Tran

Traber

Seidler

et al. 2022

Chemistry A European J

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The intense absorption of light to covering a large part of the visible spectrum is highly desirable for solar energy conversion schemes. To this end, we have developed novel anionic bis(4H‐imidazolato)Cu(I) complexes (cuprates), which feature intense, panchromatic light absorption properties throughout the visible spectrum and into the NIR region with extinction coefficients up to 28,000 M−1 cm−1. Steady‐state absorption, (spectro)electrochemical and theoretical investigations reveal low energy (Vis to NIR) metal‐to‐ligand charge‐transfer absorption bands, which are a consequence of destabilized copper‐based donor states. These high‐lying copper‐based states are induced by the σ‐donation of the chelating anionic ligands, which also feature low energy acceptor states. The optical properties are reflected in very low, copper‐based oxidation potentials and three ligand‐based reduction events. These electronic features reveal a new route to panchromatically absorbing Cu(I) complexes.

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“…These Cu(I) complexes display irregular tetrahedral coordination with bond angles ranging from 79.5(2)°to 127.51 (11)°, which are limited within a reasonable range. [45][46][47][48][49] Crystal structures…”

Section: Crystallographymentioning

confidence: 99%

Designing luminescent diimine-Cu(i)–phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra

et al. 2022

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Synthesis and characterisation of homoleptic 2,9-diaryl-1,10-phenanthroline copper(i) complexes: influencing selectivity in photoredox-catalysed atom-transfer radical addition reactions

Abstract: Novel bis(2,9-diaryl-1,10-phenanthroline)copper(i) complexes were prepared to study a photoredox-catalysed reaction.

Cited by 27 publications

References 72 publications

Long-Lived, Strongly Emissive, and Highly Reducing Excited States in Mo(0) Complexes with Chelating Isocyanides

Long-Lived, Strongly Emissive, and Highly Reducing Excited States in Mo(0) Complexes with Chelating Isocyanides

Ligand‐Induced Donor State Destabilisation – A New Route to Panchromatically Absorbing Cu(I) Complexes

Designing luminescent diimine-Cu(i)–phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra

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