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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Vydané v:	Chemistry : a European journal Ročník 27; číslo 51; s. 12959 - 12964
Hlavní autori:	Boden, Pit, Di Martino‐Fumo, Patrick, Bens, Tobias, Steiger, Sophie, Albold, Uta, Niedner‐Schatteburg, Gereon, Gerhards, Markus, Sarkar, Biprajit
Médium:	Journal Article
Jazyk:	English
Vydavateľské údaje:	Germany Wiley Subscription Services, Inc 09.09.2021 John Wiley and Sons Inc
Predmet:	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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Abstract	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.
AbstractList	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 at room temperature. These are the first examples of Cr(0), Mo(0) and W(0) complexes that emit in the NIR II region. 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. 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. 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.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. 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.
Author	Boden, Pit Bens, Tobias Sarkar, Biprajit Steiger, Sophie Gerhards, Markus Niedner‐Schatteburg, Gereon Albold, Uta Di Martino‐Fumo, Patrick
AuthorAffiliation	3 Institute of Chemistry and Biochemistry Freie Universität Berlin Fabeckstraße 34–36 14195 Berlin Germany 2 Chair of Inorganic Coordination Chemistry Institute of Inorganic Chemistry University of Stuttgart Pfaffenwaldring 55 70569 Stuttgart Germany 1 Department of Chemistry and Research Center Optimas TU Kaiserslautern Erwin-Schrödinger-Straße 52 67663 Kaiserslautern Germany
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CitedBy_id	crossref_primary_10_1021_jacs_3c03832 crossref_primary_10_1002_anie_202422702 crossref_primary_10_1016_j_ccr_2025_216454 crossref_primary_10_1002_chem_202301205 crossref_primary_10_1002_chem_202500365 crossref_primary_10_1039_D5CP00333D crossref_primary_10_1002_ange_202200653 crossref_primary_10_1002_anie_202314475 crossref_primary_10_1002_ejic_202100870 crossref_primary_10_1021_acs_inorgchem_4c05383 crossref_primary_10_1002_adsu_202401059 crossref_primary_10_1002_chem_202400730 crossref_primary_10_1021_jacs_2c04976 crossref_primary_10_1002_chem_202201038 crossref_primary_10_3390_inorganics12020046 crossref_primary_10_1039_D4QI02392G crossref_primary_10_1007_s41061_022_00386_6 crossref_primary_10_1016_j_ccr_2024_215878 crossref_primary_10_1002_ange_202422702 crossref_primary_10_1002_ange_202314475 crossref_primary_10_1002_cctc_202400024 crossref_primary_10_1002_anie_202200653 crossref_primary_10_1002_ceur_202400066 crossref_primary_10_1016_j_measurement_2025_118224 crossref_primary_10_1016_j_dyepig_2023_111087 crossref_primary_10_1002_cptc_202100296 crossref_primary_10_1007_s11696_024_03513_3
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Keywords	mesoionic carbenes X-ray diffraction step-scan FTIR spectroscopy NIR II emitters carbonyl ligands
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Snippet	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... 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...
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StartPage	12959
SubjectTerms	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
Title	NIR‐Emissive Chromium(0), Molybdenum(0), and Tungsten(0) Complexes in the Solid State at Room Temperature
URI	https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fchem.202102208 https://www.ncbi.nlm.nih.gov/pubmed/34237175 https://www.proquest.com/docview/2570387063 https://www.proquest.com/docview/2550261612 https://pubmed.ncbi.nlm.nih.gov/PMC8519045
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