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Bright Photoluminescence of [{(Cp t Bu 2 ) 2 Ce( μ ‐Cl)} 2 ]: A Valuable Technique for the Determination of the Oxidation State of Cerium
Author(s) -
Suta Markus,
Harmgarth Nicole,
Kühling Marcel,
Liebing Phil,
Edelmann Frank T.,
Wickleder Claudia
Publication year - 2018
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201701818
Subject(s) - photoluminescence , quantum yield , cerium , spectroscopy , phosphor , chemistry , ion , materials science , photoluminescence excitation , photochemistry , oxidation state , analytical chemistry (journal) , luminescence , inorganic chemistry , optoelectronics , physics , optics , catalysis , organic chemistry , fluorescence , quantum mechanics
The synthesis and photoluminescence properties of the bright‐yellow organocerium complex [{(Cpt Bu2 ) 2 Ce( μ ‐Cl)} 2 ] (Cpt Bu2 =1,3‐di( tert ‐butyl)cyclopentadienyl) are presented. This coordination compound exhibits highly efficient photoluminescence within the yellow‐light wavelength range, with a high internal quantum yield of 61(±2) % at room temperature. The large red shift is attributed to the delocalizing ability of the aromatic ligands, whilst its quantum yield even makes this compound competitive with Ce 3+ ‐activated LED phosphors in terms of its photoluminescence efficiency (disregarding its thermal stability). A bridging connection between two crystallographically independent Ce 3+ ions is anticipated to be the reason for the highly efficient photoluminescence, even up to room temperature. The emission spectrum is characterized by two bands in the orange‐light range at both 10 K and room temperature, which are attributed to the parity‐allowed transitions 5d 1 ( 2 D 3/2 )→4f 1 ( 2 F 7/2 ) and 5d 1 ( 2 D 3/2 )→4f 1 ( 2 F 5/2 ) of Ce 3+ , respectively. The photoluminescence spectra were interpreted in relation to the structure and vibrational modes of the coordination compound. The spectra and optical properties indicate that trivalent cerium ions are the dominant species in the ground state, which also resolves an often‐encountered ambiguity in organocerium compounds. This result shows that photoluminescence spectroscopy is a versatile tool that can help elucidate the oxidation state of Ce in such compounds.