Universität zu Köln

Poirier, Stephanie, Czympiel, Lisa, Belanger-Desmarais, Nicolas ORCID: 0000-0001-6992-8307, Mathur, Sanjay and Reber, Christian ORCID: 0000-0001-9350-7262 (2016). Temperature and pressure variations of d-d luminescence band maxima of bis(pyridylalkenolato)- palladium(II) complexes with different ligand substituents: opposite-signed trends. Dalton Trans., 45 (15). S. 6574 - 6582. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1477-9234

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Abstract

Luminescence spectra of two d(8)-configured bis(pyridylalkenolato) palladium(II) complexes, [Pd{PyCHC-(C3F7)O}(2)] and [Pd{PyCHC(CH3)O}(2)], are presented at variable temperature and pressure. Bands are assigned as d-d transitions. The heptafluoropropyl and methyl substituents on the ligands have different steric demands, influencing luminescence spectra. Broad bands with maxima at approximately 12 700 cm(-1) (790 nm) for ligands with heptafluoropropyl substituents and 12 100 cm(-1) (830 nm) for ligands with methyl substituents and widths of approximately 2100 cm(-1) for both complexes are observed at 80 K. Quenching of the luminescence is observed as temperature increases. The maxima of [Pd{PyCHC(C3F7)O}(2)] show a shift of -0.9 +/- 0.1 cm(-1) K-1 due to broadening of the spectra to lower energy. The luminescence maxima of [Pd{PyCHC(CH3)O}(2)] shift in the opposite direction by + 7.2 +/- 0.7 cm(-1) K-1. Shifts with different signs are also obtained from variable-pressure luminescence spectra, with values of + 13 +/- 2 cm(-1) kbar(-1) and -15 +/- 7 cm(-1) kbar(-1) for [Pd{PyCHC(C3F7)O}(2)] and [Pd{PyCHC(CH3)O}(2)], respectively. The pressure-induced decrease is unusual and likely caused by intermolecular interactions involving the palladium(II) center and a vinylic proton of a neighboring complex.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Poirier, Stephanie UNSPECIFIED UNSPECIFIED UNSPECIFIED Czympiel, Lisa UNSPECIFIED UNSPECIFIED UNSPECIFIED Belanger-Desmarais, Nicolas UNSPECIFIED orcid.org/0000-0001-6992-8307 UNSPECIFIED Mathur, Sanjay UNSPECIFIED UNSPECIFIED UNSPECIFIED Reber, Christian UNSPECIFIED orcid.org/0000-0001-9350-7262 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-290309
DOI:	10.1039/c5dt05068e
Journal or Publication Title:	Dalton Trans.
Volume:	45
Number:	15
Page Range:	S. 6574 - 6582
Date:	2016
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1477-9234
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language EMITTING-STATE PROPERTIES; TRANSITION-METAL; ABSORPTION-SPECTRA; RAMAN-SPECTROSCOPY; SQUARE-PLANAR; PLATINUM(II); INTENSITIES; DEPENDENCE; EMISSION; EXCHANGE Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/29030