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Energy Dispersive XAFS: Characterization of Electronically Excited States of Copper(I) Complexes

DOI: 10.1021/jp4020355 DOI Help
PMID: 23718738 PMID Help

Authors: Moniek Tromp (Southampton University) , Andrew Dent (Diamond Light Source Ltd) , Jon Headspith (Science and Technology Facilities Council (STFC)) , Timothy Easun (University of Nottingham) , Xue-zhong Sun (University of Nottingham) , Michael George (University of Nottingham) , Olivier Mathon (ESRF) , Grigory Smolentsev (Paul Scherrer Institute, Villigen) , Michelle Hamilton (University of Nottingham; Research Complex at Harwell) , John Evans (Research Complex at Harwell, Chemistry, University of Southampton, Diamond Light Source)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: The Journal Of Physical Chemistry B , VOL 117 (24) , PAGES 7381 - 7387

State: Published (Approved)
Published: June 2013

Open Access Open Access

Abstract: Energy dispersive X-ray absorption spectroscopy (ED-XAS), in which the whole XAS spectrum is acquired simultaneously, has been applied to reduce the real-time for acquisition of spectra of photoinduced excited states by using a germanium microstrip detector gated around one X-ray bunch of the ESRF (100 ps). Cu K-edge XAS was used to investigate the MLCT states of [Cu(dmp)2]+ (dmp =2,9-dimethyl-1,10-phenanthroline) and [Cu(dbtmp)2]+ (dbtmp =2,9-di-n-butyl-3,4,7,8-tetramethyl-1,10-phenanthroline) with the excited states created by excitation at 450 nm (10 Hz). The decay of the longer lived complex with bulky ligands, was monitored for up to 100 ns. DFT calculations of the longer lived MLCT excited state of [Cu(dbp)2]+ (dbp =2,9-di-n-butyl-1,10-phenanthroline) with the bulkier diimine ligands, indicated that the excited state behaves as a Jahn–Teller distorted Cu(II) site, with the interligand dihedral angle changing from 83 to 60° as the tetrahedral coordination geometry flattens and a reduction in the Cu–N distance of 0.03 Å.

Journal Keywords: Energy Dispersive Xafs: Characterization Of Electronically Excited States Of Copper(I) Complexes

Subject Areas: Physics, Technique Development, Materials

Facility: ESRF