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:
CreatorsEmailORCIDORCID Put Code
Poirier, StephanieUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Czympiel, LisaUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Belanger-Desmarais, NicolasUNSPECIFIEDorcid.org/0000-0001-6992-8307UNSPECIFIED
Mathur, SanjayUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Reber, ChristianUNSPECIFIEDorcid.org/0000-0001-9350-7262UNSPECIFIED
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: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
EMITTING-STATE PROPERTIES; TRANSITION-METAL; ABSORPTION-SPECTRA; RAMAN-SPECTROSCOPY; SQUARE-PLANAR; PLATINUM(II); INTENSITIES; DEPENDENCE; EMISSION; EXCHANGEMultiple languages
Chemistry, Inorganic & NuclearMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/29030

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