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Near-Infrared Luminescence in Trinuclear Mixed-Metal Chalcogenolate Complexes of the Types [M$_{2}$Ti(EPh)$_{6}$(PPh$_{3}$)$_{2}$] (M = Cu, Ag; E = S, Se) and [Na(thf)$_{3}$]$_{2}$[Ti(SPh)$_{6}$]

Lebedkin, Sergei 1; Weigend, Florian 1; Eichhöfer, Andreas 1
1 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)


The optical properties of four new trinuclear chalcogenolato bridged metal complexes [Ag$_{2}$Ti(SPh)$_{6}$(PPh$_{3}$)$_{2}$], [Na(thf)$_{3}$]$_{2}$[Ti(SPh)$_{6}$], [Cu$_{2}$Ti(SePh)$_{6}$(PPh$_{3}$)$_{2}$], and [Ag$_{2}$Ti(SePh)$_{6}$(PPh$_{3}$)$_{2}$] have been investigated by absorption and photoluminescence spectroscopy as well as time-dependent density functional theory (TDDFT) calculations and compared to the results published recently for [Cu$_{2}$Ti(SPh)$_{6}$(PPh$_{3}$)$_{2}$]. All of these compounds are distinguished by efficient near-infrared luminescence at ∼880–1200 nm in the solid state at low temperatures, which remains quite intense for the copper–titanium complexes at ambient temperature with PL quantum yields of 9.5 and 4.8% at λPL = 1090 and 1240 nm for [Cu$_{2}$Ti(EPh)$_{6}$(PPh$_{3}$)$_{2}$], E = S, Se, respectively. According to the calculations, a peculiar feature of the lowest-energy electronic transitions in these complexes is their high localization on the metal and chalcogen atoms, with negligible contributions of the “external” ligand groups. Correspondingly, the type of atoms in the M$_{2}$TiE$_{6}$ (M = Cu, Ag, Na) core structure determines optical properties such as the absorption and emission wavelengths and PL lifetime.

Postprint §
DOI: 10.5445/IR/1000140115
Veröffentlicht am 11.06.2022
DOI: 10.1021/acs.inorgchem.1c00829
Zitationen: 3
Web of Science
Zitationen: 2
Zitationen: 3
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsmonat/-jahr 06.2021
Sprache Englisch
Identifikator ISSN: 0020-1669, 1520-510X
KITopen-ID: 1000140115
HGF-Programm 43.32.01 (POF IV, LK 01) Molecular Materials Basis for Optics & Photonics
Weitere HGF-Programme 43.31.01 (POF IV, LK 01) Multifunctionality Molecular Design & Material Architecture
Erschienen in Inorganic chemistry
Verlag American Chemical Society (ACS)
Band 60
Heft 12
Seiten 8936–8945
Vorab online veröffentlicht am 10.06.2021
Schlagwörter 2014-013-004856 SCXD
Nachgewiesen in Dimensions
Web of Science
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