NIR‐Emissive Chromium(0), Molybdenum(0), and Tungsten(0) Complexes in the Solid State at Room Temperature

The development of NIR emitters based on earth‐abundant elements is an important goal in contemporary science. We present here Cr(0), Mo(0), and W(0) carbonyl complexes with a pyridyl‐mesoionic carbene (MIC) based ligand. A detailed photophysical investigation shows that all the complexes exhibit du...

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Vydáno v:Chemistry : a European journal Ročník 27; číslo 51; s. 12959 - 12964
Hlavní autoři: Boden, Pit, Di Martino‐Fumo, Patrick, Bens, Tobias, Steiger, Sophie, Albold, Uta, Niedner‐Schatteburg, Gereon, Gerhards, Markus, Sarkar, Biprajit
Médium: Journal Article
Jazyk:angličtina
Vydáno: Germany Wiley Subscription Services, Inc 09.09.2021
John Wiley and Sons Inc
Témata:
Atomic energy levels
Carbonyl compounds
carbonyl ligands
Carbonyls
Chemistry
Chromium
Communication
Communications
Density functional theory
Emissions
Emissivity
Emitters
mesoionic carbenes
Molybdenum
NIR II emitters
Room temperature
step-scan FTIR spectroscopy
Triplet state
Tungsten
X-ray diffraction
mesoionic carbenes
X-ray diffraction
step-scan FTIR spectroscopy
NIR II emitters
carbonyl ligands
ISSN:0947-6539, 1521-3765, 1521-3765
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Shrnutí:The development of NIR emitters based on earth‐abundant elements is an important goal in contemporary science. We present here Cr(0), Mo(0), and W(0) carbonyl complexes with a pyridyl‐mesoionic carbene (MIC) based ligand. A detailed photophysical investigation shows that all the complexes exhibit dual emissions in the VIS and in the NIR region. The emissive excited states are assigned to two distinct triplet states by time‐resolved emission and step‐scan FTIR spectroscopy at variable temperature, supported by density functional theory. In particular, the NIR emissive triplet state exhibits unprecedented lifetimes of up to 600±10 ns and quantum yields reaching 1.7 ⋅ 10−4 at room temperature. These are the first examples of Cr(0), Mo(0) and W(0) complexes that emit in the NIR II region. This work presents emissive Cr(0), Mo(0), and W(0) complexes that contain a bidentate pyridyl‐mesoionic carbene ligand and CO coligands. These systems exhibit dual vis and NIR II emissions at room temperature. The emissive excited triplet states were characterized by temperature‐dependent luminescence and step‐san FTIR spectroscopy in combination with density functional theory. The NIR quantum yield increases from Cr(0) over Mo(0) to W(0), reaching a very high value of 1.4 ⋅ 10−3 at room temperature.
Bibliografie:In memory of Markus Gerhards.
Deceased.
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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202102208