Trigonal Copper(I) Complexes with Cyclic (Alkyl)(amino)carbene Ligands for Single-Photon Near-IR Triplet Emission

Molecular near-IR (NIR) triplet-state emitters are of importance for the development of new, organic-electronics-based telecommunication technologies as optical fibers operating in the corresponding spectral bands allow for data transfer over much longer distances due to the significantly lower atte...

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Veröffentlicht in:Inorganic chemistry 2022-09, Vol.61 (37), p.14833-14844
Hauptverfasser: Muthig, André M. T., Krumrein, Marcel, Wieland, Justin, Gernert, Markus, Kerner, Florian, Pflaum, Jens, Steffen, Andreas
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container_end_page 14844
container_issue 37
container_start_page 14833
container_title Inorganic chemistry
container_volume 61
creator Muthig, André M. T.
Krumrein, Marcel
Wieland, Justin
Gernert, Markus
Kerner, Florian
Pflaum, Jens
Steffen, Andreas
description Molecular near-IR (NIR) triplet-state emitters are of importance for the development of new, organic-electronics-based telecommunication technologies as optical fibers operating in the corresponding spectral bands allow for data transfer over much longer distances due to the significantly lower attenuation. However, achieving such low-energy triplet excited states with good radiative rate constants is very challenging, and studies regarding the single-photon emission of organometallics in this energy range are scarce. We have prepared a series of trigonal CuI CAAC complexes bearing chelating ligands with O, N, S, and Se donor atoms and studied their photophysical properties in this context. The compounds show weak low-energy absorption in solution between 400 and 500 nm due to mixed Cu → CAAC 1MLCT/LLCT states, resulting in yellow-green to orange appearance, which we have also correlated to the 15N NMR resonances of the π-accepting carbene ligand. In the solid state, phosphorescence from dominant 3(Cu → CAAC) CT states is observed at room temperature. The emission of the complexes is bathochromically shifted in comparison to structurally related linearly coordinated copper­(I) CAAC complexes due to structural reorganization in the excited state to a T-shape. For [Cu­(dbm)­(CAACMe)], the broad phosphorescence with outstanding λmax = 760 nm tailors out to ca. 1100 nm and leads to its proof-of-concept application as a nonclassical single-photon light source, constituting key functional units for the implementation of tap-proof data transfer.
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The compounds show weak low-energy absorption in solution between 400 and 500 nm due to mixed Cu → CAAC 1MLCT/LLCT states, resulting in yellow-green to orange appearance, which we have also correlated to the 15N NMR resonances of the π-accepting carbene ligand. In the solid state, phosphorescence from dominant 3(Cu → CAAC) CT states is observed at room temperature. The emission of the complexes is bathochromically shifted in comparison to structurally related linearly coordinated copper­(I) CAAC complexes due to structural reorganization in the excited state to a T-shape. 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title Trigonal Copper(I) Complexes with Cyclic (Alkyl)(amino)carbene Ligands for Single-Photon Near-IR Triplet Emission
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