Transferring the entatic-state principle to copper photochemistry

Dicke, Benjamin; Hoffmann, Alexander; Stanek, Julia; Rampp, Michael S.; Grimm‐Lebsanft, Benjamin; Biebl, Florian; Rukser, Dieter; Maerz, Benjamin; Göries, Dennis; Naumova, Maria; Biednov, Mykola; Neuber, G.; Wetzel, Alina; Hofmann, Stefan; Roedig, Philip; Meents, A.; Bielecki, Johan; Andreasson, Jakob; Beyerlein, Kenneth R.; Chapman, Henry N.; Bressler, Christian; Zinth, Wolfgang; Rübhausen, Michael; Herres‐Pawlis, Sonja

doi:10.1038/nchem.2916

Cited by 64 publications

(76 citation statements)

References 56 publications

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“…All in all, these observations seem to be in relation to the entatic state principle, which describes a pre‐organization of the ligand sphere in order to stabilize a certain coordination mode. This structural pre‐distortion is known for Cu I complexes in a protein matrix, as well as for other synthetically Cu I complexes, for example, Cu I complexes with guanidine ligands or heteroleptic Cu I complexes with sterically demanding phenanthroline ligands …”

Section: Resultsmentioning

confidence: 93%

Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties

Giereth

Mengele

Frey

et al. 2020

Chemistry A European J

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A series of seven homoleptic CuI complexes based on hetero‐bidentate P^N ligands was synthesized and comprehensively characterized. In order to study structure–property relationships, the type, size, number and configuration of substituents at the phosphinooxazoline (phox) ligands were systematically varied. To this end, a combination of X‐ray diffraction, NMR spectroscopy, steady‐state absorption and emission spectroscopy, time‐resolved emission spectroscopy, quenching experiments and cyclic voltammetry was used to assess the photophysical and electrochemical properties. Furthermore, time‐dependent density functional theory calculations were applied to also analyze the excited state structures and characteristics. Surprisingly, a strong dependency on the chirality of the respective P^N ligand was found, whereas the specific kind and size of the different substituents has only a minor impact on the properties in solution. Most importantly, all complexes except C3 are photostable in solution and show fully reversible redox processes. Sacrificial reductants were applied to demonstrate a successful electron transfer upon light irradiation. These properties render this class of photosensitizers as potential candidates for solar energy conversion issues.

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Section: Resultsmentioning

confidence: 93%

Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties

Giereth

Mengele

Frey

et al. 2020

Chemistry A European J

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“…The chemical reversibility of the Cu I/II transition allowed us to study both forms in their stable configurations using an optically transparent thin‐layer electrolysis (OTTLE) cell …”

Section: Resultsmentioning

confidence: 99%

“…Typical square scheme behavior for Cu I /Cu II pairs with non‐entatic state properties, i.e. different and effectively separated coordination structures, was observed by cyclic voltammetry and analyzed through simulations, using kinetic and thermodynamic parameters.…”

Section: Discussionmentioning

confidence: 99%

Hybrid α‐Diimine/Bis(chalcogenoether) Ligands for Copper(I) and Copper(II) Complexes

Bubrin

Kvapilová

Fiedler

et al. 2018

Zeitschrift anorg allge chemie

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The new ligands L = 1,4‐bis(2‐methylchalcogenophenyl)‐2,3‐dimethyl‐1,4‐diaza‐1,3‐diene [chalcogen = O (1), S (2) or Se (3)] have been studied in their coordination behavior towards CuI and CuII. Whereas the O‐ether containing ligand forms complex ions [Cu(L)2]n+ = 4n+, with exclusive N‐coordination (n = 1) or N and weaker O coordination (n = 2), the species with E = S or Se contain tetradentate ligands in [Cu(L)]+ (5+, 6+) and [Cu(L)L′]n+ [n = 1, L′ = TfO– (E = S) or n = 2 and L′ = H2O (E = Se)]. Molecular structures in the crystals of 5+ and 6+ show distorted tetrahedral N coordination at the metal and innocently behaving α‐diimine functions, in agreement with spectroscopic and computational data. The copper(II) ions [Cu(L)L′]2+ with one tetradentate ligand L = 2 or 3 exhibit a square‐pyramidal configuration at the metal. Two isolated crystalline forms of 42+ show weak coordination (2.636–2.96 Å) of three or four ether oxygen atoms, resulting in 4+3 or 4+4 coordination arrangements for N and O donors, respectively. In agreement with the rather different CuI and CuII structures the electrochemical oxidation of the copper(I) complexes and the reduction of the corresponding CuII species reveal an ECEC behavior within a square scheme, whereas the reduction of the CuI compounds, most likely at the diimine site, proceeds irreversibly. UV/Vis spectroelectrochemical results showing intense MLCT and IL absorptions were analyzed with the help of TD‐DFT calculations.

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“…[8,11] The already reported catalysts B, C,a nd D afforded the desired product 2a in moderate yields (22-25 %, entries 2-4). The heteroleptic complexes E and F,w hich are based on ag uanidine-quinoline (DMEGqu) and a biphosphine ligand [22,24] designed during the course of this study,a fforded similar results, albeit with al ower conversiono f the starting material 1a (approx. 60 %).…”

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confidence: 89%

Copper‐Photocatalyzed Borylation of Organic Halides under Batch and Continuous‐Flow Conditions

Nitelet

Thévenet²,

Schiavi³

et al. 2019

Chemistry A European J

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The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides( Ia nd Br) was reported. The reaction proceededu sing an ew heteroleptic Cu complex under irradiation with blue LEDs, givingt he corresponding boronic-acid esters in good to excellent yields. The reactionw as extended to continuous-flowc onditions to allow an easy scale-up. The mechanism of the reaction was studied and am echanism based on ar eductive quenching (Cu I /Cu I */Cu 0 )w as suggested.

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Transferring the entatic-state principle to copper photochemistry

Cited by 64 publications

References 56 publications

Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties

Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties

Hybrid α‐Diimine/Bis(chalcogenoether) Ligands for Copper(I) and Copper(II) Complexes

Copper‐Photocatalyzed Borylation of Organic Halides under Batch and Continuous‐Flow Conditions

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