Light‐Induced Ejection of a Tridentate Ligand from a Ruthenium(II) Complex

Awada, Ali; Jouvenot, Damien

doi:10.1002/ejic.202100607

Cited by 4 publications

(4 citation statements)

References 29 publications

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“…In this contribution we report the synthesis, characterization, and photochemical reactivity of complexes of the ligands 1-(2-picolyl)-4-phenyl-1,2,3-triazole (pictz) and bis(4-phenyl-1,2,3-triazol-1-yl)methane (btzm) in which the triazole-containing ligands additionally contain a methylene bridge between their donor heterocycles thus resulting in more flexible 6-membered chelate rings (Figure ). Here, we envisaged that the expanded chelate ring formed by these ligands would confer greater excited-state conformational freedom, which might result in increased photochemical reactivity which has been shown with other systems that feature diamine and thioether-based departing ligands that form 6-membered chelate rings. ,− We show that these complexes indeed undergo relatively efficient photochemical ejection of the triazole-containing ligand and provide spectroscopic evidence of the formation of monodentate ligand-loss solvent complex intermediates. Further, we show that in these monodentate complexes, linkage isomerism can be induced whereby the triazole-containing ligand converts from the initial coordination mode via the N2-position to become coordinated by the more basic N3 atom.…”

Section: Introductionmentioning

confidence: 53%

Photochemistry of Ru(II) Triazole Complexes with 6-Membered Chelate Ligands: Detection and Reactivity of Ligand-Loss Intermediates

Eastham,

Kennedy,

Scottwell

et al. 2024

Inorg. Chem.

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Photochemical ligand release from metal complexes may be exploited in the development of novel photoactivated chemotherapy agents for the treatment of cancer and other diseases. Highly intriguing photochemical behavior is reported for two ruthenium(II) complexes bearing conformationally flexible 1,2,3triazole-based ligands incorporating a methylene spacer to form 6membered chelate rings. [Ru(bpy) 2 (pictz)] 2+ (1) and [Ru-(bpy) 2 (btzm)] 2+ (2) (bpy = 2,2′-bipyridyl; pictz = 1-(picolyl)-4phenyl-1,2,3-triazole; btzm = bis(4-phenyl-1,2,3-triazol-4-yl)methane) exhibit coordination by the triazole ring through the less basic N2 atom as a consequence of chelation and readily undergo photochemical release of the pictz and btzm ligands (ϕ = 0.079 and 0.091, respectively) in acetonitrile solution to form cis-[Ru-(bpy) 2 (NCMe) 2 ] 2+ (3) in both cases. Ligand-loss intermediates of the form [Ru(bpy) 2 (κ 1 -pictz or κ 1 -btzm)(NCCD 3 )] 2+ are detected by 1 H NMR spectroscopy and mass spectrometry. Photolysis of 1 yields three ligand-loss intermediates with monodentate pictz ligands, two of which form through simple decoordination of either the pyridine or triazole donor with subsequent solvent coordination (4-tz (N2) and 4-py, respectively). The third intermediate, shown to be able to form photochemically directly from 1, arises through linkage isomerism in which the monodentate pictz ligand is coordinated by the triazole N3 atom (4-tz (N3) ) with a comparable ligand-loss intermediate with an N3-bound κ 1 -btzm ligand also observed for 2.

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Section: Introductionmentioning

confidence: 53%

Photochemistry of Ru(II) Triazole Complexes with 6-Membered Chelate Ligands: Detection and Reactivity of Ligand-Loss Intermediates

Eastham,

Kennedy,

Scottwell

et al. 2024

Inorg. Chem.

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“…White light irradiation of a solution of RU7 in MeCN resulted in alterations in the absorption spectrum consistent with formation of the solvate complex and ejection of btap. 10…”

Section: Poly- and Pyridine-based Ligand Dissociationmentioning

confidence: 99%

“…8,9 However, also within the broad envelope of PDT is the class of PACs for which light stimulation directly affects their core components to result in the ejection of a molecule. 10…”

Section: Introductionmentioning

confidence: 99%

“…8,9 However, also within the broad envelope of PDT is the class of PACs for which light stimulation directly affects their core components to result in the ejection of a molecule. 10 The released molecule may have a direct therapeutic effect or play a key role in various physiological processes. 11 Since light can be highly focused and directed to a specific site the photorelease process can offer both spatial and temporal control for a therapy.…”

Section: Introductionmentioning

confidence: 99%

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Recent advances in photorelease complexes for therapeutic applications

Benniston

Zeng

2022

Dalton Trans.

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Synthesis of Phosphorus/Arsenic Tridentate Ligands and Their Application for Luminescent Copper (I) Halide Complexes

Shimoji,

Kihara,

Sumida

et al. 2024

Eur J Inorg Chem

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We synthesized arsenic analogs of a tridentate PPP ligand, bis[2‐(diphenylphosphino)phenyl]phenylphosphine, achieving yields of 40% to 71%. Additionally, we prepared copper(I) halide (CuX, X = Br, I) complexes with these ligands, with yields between 43% and 84%. Using both experimental and computational methods, we examined their structures and photophysical characteristics. Single crystal X‐ray diffraction showed that all eight complexes had distorted tetrahedral geometries. These complexes exhibited photoluminescence with emission bands peaking from 506 nm to 551 nm and quantum yields up to 0.92 at room temperature. Emission lifetimes varied and showed no direct correlation with quantum yields or wavelengths. Physical manipulation and solvent variations significantly altered their photoluminescent properties. DFT and TD‐DFT calculations revealed that higher arsenic content increased spin‐orbit coupling constants, with iodide complexes performing better than bromide ones due to heavier elements enhancing spin‐orbit coupling. Substituting phosphorus with arsenic significantly affected the luminescence quantum yield and lifetime, demonstrating the heavy‐atom effect of arsenic. The position of arsenic in the ligands critically influenced the photophysical outcomes of the CuX complexes.

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Light‐Induced Ejection of a Tridentate Ligand from a Ruthenium(II) Complex

Cited by 4 publications

References 29 publications

Photochemistry of Ru(II) Triazole Complexes with 6-Membered Chelate Ligands: Detection and Reactivity of Ligand-Loss Intermediates

Photochemistry of Ru(II) Triazole Complexes with 6-Membered Chelate Ligands: Detection and Reactivity of Ligand-Loss Intermediates

Recent advances in photorelease complexes for therapeutic applications

Synthesis of Phosphorus/Arsenic Tridentate Ligands and Their Application for Luminescent Copper (I) Halide Complexes

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