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Ultrafast electronic, infrared, and X-ray absorption spectroscopy study of Cu(i) phosphine diimine complexes

DOI: 10.1039/D3FD00027C DOI Help

Authors: Martin V. Appleby (The University of Sheffield) , Rory A. Cowin (The University of Sheffield) , Iona Ivalo (The University of Sheffield) , Samantha L. Peralta-Arriaga (The University of Sheffield) , Craig C. Robertson (The University of Sheffield) , Stuart Bartlett (Diamond Light Source) , Ann Fitzpatrick (Diamond Light Source) , Andrew Dent (Diamond Light Source) , Gabriel Karras (Diamond Light Source) , Sofia Diaz-Moreno (Diamond Light Source) , Dimitri Chekulaev (The University of Sheffield) , Julia A. Weinstein (University of Sheffield)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Faraday Discussions , VOL 1

State: Published (Approved)
Published: July 2023
Diamond Proposal Number(s): 28403 , 30784

Open Access Open Access

Abstract: The study aims to understand the role of the transient bonding in the interplay between the structural and electronic changes in heteroleptic Cu(I) diimine diphosphine complexes. This is an emerging class of photosensitisers which absorb in the red region of the spectrum, whilst retaining a sufficiently long excited state lifetime. Here, the dynamics of these complexes are explored by transient absorption (TA) and time-resolved infrared (TRIR) spectroscopy, which reveal ultrafast intersystem crossing and structural distortion occurring. Two potential mechanisms affecting excited state decay in these complexes involve a transient formation of a solvent adduct, made possible by the opening up of the Cu coordination centre in the excited state due to structural distortion, and by a transient coordination of the O-atom of the phosphine ligand to the copper center. X-ray absorption studies of the ground electronic state have been conducted as a prerequisite for the upcoming X-ray spectroscopy studies which will directly determine structural dynamics. The potential for these complexes to be used in bimolecular applications is confirmed by a significant yield of singlet oxygen production.

Subject Areas: Chemistry

Instruments: I18-Microfocus Spectroscopy

Added On: 14/07/2023 11:22


Discipline Tags:

Molecular Complexes Physical Chemistry Chemistry Inorganic Chemistry

Technical Tags:

Spectroscopy X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS)