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 |
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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. |
doi_str_mv | 10.1021/acs.inorgchem.2c02376 |
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T. ; Krumrein, Marcel ; Wieland, Justin ; Gernert, Markus ; Kerner, Florian ; Pflaum, Jens ; Steffen, Andreas</creator><creatorcontrib>Muthig, André M. T. ; Krumrein, Marcel ; Wieland, Justin ; Gernert, Markus ; Kerner, Florian ; Pflaum, Jens ; Steffen, Andreas</creatorcontrib><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.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/acs.inorgchem.2c02376</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Inorganic chemistry, 2022-09, Vol.61 (37), p.14833-14844</ispartof><rights>2022 The Authors. 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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.</description><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkE1LwzAYx4MoOKcfQcixO3Q-Sfp6HGPqYKjoDt5KmqZdZtp0SYfu25ux4dXT84fn_wI_hO4JTAlQ8sCFm6rO2EZsZDulAihLkws0IjGFMCbweYlGAF6TJMmv0Y1zWwDIWZSM0G5tVWM6rvHc9L20wXLiVdtr-SMd_lbDBs8PQiuBg5n-OuhJwFu_NRHclrKTeKUa3lUO18biD9U1WoZvGzOYDr9IbsPlO_YDvm3Ai1Y5p0x3i65qrp28O98xWj8u1vPncPX6tJzPViGncTaEJKqgqikDVhJKIxIRkbI6zkiZlnnF0oiWLIEM8iiBlMVpnJCaiTLKMi-znI1RcKrtrdntpRsKvy-k1ryTZu8KmhLCIKfx0RqfrMIa56ysi96qlttDQaA4Ei484eKPcHEm7HPklDu-t2ZvPUb3T-YXX3iCEg</recordid><startdate>20220919</startdate><enddate>20220919</enddate><creator>Muthig, André M. 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T. ; Krumrein, Marcel ; Wieland, Justin ; Gernert, Markus ; Kerner, Florian ; Pflaum, Jens ; Steffen, Andreas</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a258t-14d0df2303b1224141c73f581b7b9d3742b3608094607357561f3cb488756893</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Muthig, André M. 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Chem</addtitle><date>2022-09-19</date><risdate>2022</risdate><volume>61</volume><issue>37</issue><spage>14833</spage><epage>14844</epage><pages>14833-14844</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>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.</abstract><pub>American Chemical Society</pub><doi>10.1021/acs.inorgchem.2c02376</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0002-3733-1095</orcidid><orcidid>https://orcid.org/0000-0002-6952-7391</orcidid><orcidid>https://orcid.org/0000-0001-5326-8244</orcidid></addata></record> |
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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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