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A Tris(diisocyanide)chromium(0) Complex Is a Luminescent Analog of [Fe(2,2'-Bipyridine)3]2+

Büldt, Laura A. and Guo, Xingwei and Vogel, Raphael and Prescimone, Alessandro and Wenger, Oliver S.. (2017) A Tris(diisocyanide)chromium(0) Complex Is a Luminescent Analog of [Fe(2,2'-Bipyridine)3]2+. Journal of the American Chemical Society, 139 (2). pp. 985-992.

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Abstract

A meta-terphenyl unit was substituted with an isocyanide group on each of its two terminal aryls to afford a bidentate chelating ligand (CNtBuAr3NC) that is able to stabilize chromium in its zerovalent oxidation state. The homoleptic Cr(CNtBuAr3NC)3 complex luminesces in solution at room temperature, and its excited-state lifetime (2.2 ns in deaerated THF at 20 °C) is nearly 2 orders of magnitude longer than the current record lifetime for isoelectronic Fe(II) complexes, which are of significant interest as earth-abundant sensitizers in dye-sensitized solar cells. Due to its chelating ligands, Cr(CNtBuAr3NC)3 is more robust than Cr(0) complexes with carbonyl or monodentate isocyanides, manifesting in comparatively slow photodegradation. In the presence of excess anthracene in solution, efficient energy transfer and subsequent triplet–triplet annihilation upconversion is observed. With an excited-state oxidation potential of −2.43 V vs Fc+/Fc, the Cr(0) complex is a very strong photoreductant. The findings presented herein are relevant for replacement of precious metals in dye-sensitized solar cells and in luminescent devices by earth-abundant elements.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Büldt, Laura Allegra and Guo, Xingwei and Vogel, Raphael and Prescimone, Alessandro
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:11 Jun 2018 09:10
Deposited On:16 Apr 2018 07:42

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