Heteroleptic Copper(I)-Based Complexes Incorporating BINAP and π-Extended Diimines: Synthesis, Catalysis and Biological Applications

Cruché, Corentin; Gupta, Sayak; Kodanko, Jeremy J.; Collins, Shawn K.

doi:10.3390/molecules27123745

Cited by 3 publications

(2 citation statements)

References 40 publications

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“…Diimine copper(I) complexes featuring a 2,9-dimethylphenanthroline (dmp, NN 2 ) or a 2,2′-biquinoline (biq, NN 424 ) combined with methyldiphenylphospine or dppe ( PP 55 ) were recently synthesized and characterized, with the methyldiphenylphosphine ligand resulting in more stable complexes in solution compared to triphenylphosphine due to a better σ-donation and a smaller Tolman cone angle while complexes based on dppe equilibrated to the corresponding homoleptic complexes . A series of heteroleptic diimine-Binap copper(I) complexes [Cu( NN )( PP 41 )]BF 4 with π-extended diimine ligands including dpq (bis(desmethyl) analogue of ddpq NN 195 ), dppz ( NN 197 ) and bdppz (bis(desmethyl) analogue of NN 251 ) were synthesized and characterized . They were shown to display acceptable levels of activity for the reductive debromination of an alkyl bromide but negligible activity in PCET or ET processes.…”

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Photoactive Copper Complexes: Properties and Applications

et al. 2022

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Photocatalyzed and photosensitized chemical processes have seen growing interest recently and have become among the most active areas of chemical research, notably due to their applications in fields such as medicine, chemical synthesis, material science or environmental chemistry. Among all homogeneous catalytic systems reported to date, photoactive copper(I) complexes have been shown to be especially attractive, not only as alternative to noble metal complexes, and have been extensively studied and utilized recently. They are at the core of this review article which is divided into two main sections. The first one focuses on an exhaustive and comprehensive overview of the structural, photophysical and electrochemical properties of mononuclear copper(I) complexes, typical examples highlighting the most critical structural parameters and their impact on the properties being presented to enlighten future design of photoactive copper(I) complexes. The second section is devoted to their main areas of application (photoredox catalysis of organic reactions and polymerization, hydrogen production, photoreduction of carbon dioxide and dye-sensitized solar cells), illustrating their progression from early systems to the current state-of-the-art and showcasing how some limitations of photoactive copper(I) complexes can be overcome with their high versatility.

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confidence: 99%

Photoactive Copper Complexes: Properties and Applications

et al. 2022

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“…Concerning the effect of the extension of the π-system of redox-active ligands, experimental data are puzzling; there are certain instances when it affects the photophysical properties and reactivity of transition metal complexes. − This observation fits the notion that delocalization throughout the extended π-system is expected to make the storing an additional electron/radical “easier.” Yet, there are plenty of counterintuitive experimental data (Figure b) as well, showing, for example, that the fusion of C 6 -rings to the backbone of bpy (i.e., [Ru(bpy) 3 ] 2+ vs [Ru(phen) 3 ] 2+ ) has a negligible effect on the thermodynamics of ligand-centered ground- and excited-state redox events ( E 0 red and * E 0 ox ). − …”

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confidence: 97%

Fusion Position-Dependent Aromatic Transitions of Ligand Backbone Rings for Controlling the Redox Energetics of Photoredox Catalysts

Girnt,

Molina-Aguirre,

Gomez Bustos

et al. 2024

Inorg. Chem.

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To reveal, quantify, and rationalize the effect of backbone π-extension on ligand redox activity, we studied the ground-and excited-state reduction potentials of eight ruthenium photoredox catalysts with the formula Ru(ppy) 2 L (L is the redox-active ligand of the bipyridine family) using density functional theory. Our research underlines the profound importance of the fusion position of backbone aromatic C 6 rings on the redox activity of ligands in transition metal photoredox catalysts. Namely, certain fusion positions lead to the dearomatization of C 6 rings in ligand-centered electron transfer events, resulting in a thermodynamic penalty equivalent to a half-volt negative shift in the reduction potential. Contrarily, the extent of backbone delocalization shows a minimal impact on redox energetics, which can be explained by the charge concentration at the nitrogen contact atoms in ligand-centered reductions. Grounded in Caulton's conceptual framework, we reaffirm the predictive potency of Lewis structures in ligand-centered redox energetics with qualitative and quantitative data. Our hypothesis regarding the effect of backbone ring dearomatization on redox energetics is further corroborated using magnetic and structure-based aromaticity indicators. Highlighting fusion-dependent dearomatization as a determining factor of ligand-centered electron transfer energetics, our findings hold implications for molecular-level design in advanced electroactive materials and catalysts.

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Structure‐Property Relationships in a New Family of Photoactive Diimine‐Diphosphine Copper(I) Complexes

Beaudelot

Evano

Moucheron

2023

Chemistry A European J

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A new family of heteroleptic diimine‐diphosphine copper(I) complexes is reported, with six new complexes compared to benchmark [Cu(bcp)(DPEPhos)]PF6. These new complexes are based on 1,4,5,8‐tetraazaphenanthrene (TAP) ligands with representative electronic properties as well as substitution patterns and DPEPhos and XantPhos as diphosphine ligands. Their photophysical and electrochemical properties were investigated and correlated with the number and position of substituents on the TAP ligands. Stern‐Volmer studies using Hünig's base as reductive quencher demonstrated the influence of the complex photoreduction potential and of the excited state lifetime on the photoreactivity. This study refines the structure‐property relationship profile for heteroleptic copper(I) complexes and confirms that such profiles are of high interest to design new copper complexes as optimized photoredox catalysts.

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Heteroleptic Copper(I)-Based Complexes Incorporating BINAP and π-Extended Diimines: Synthesis, Catalysis and Biological Applications

Cited by 3 publications

References 40 publications

Photoactive Copper Complexes: Properties and Applications

Photoactive Copper Complexes: Properties and Applications

Fusion Position-Dependent Aromatic Transitions of Ligand Backbone Rings for Controlling the Redox Energetics of Photoredox Catalysts

Structure‐Property Relationships in a New Family of Photoactive Diimine‐Diphosphine Copper(I) Complexes

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