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Media type:
E-Article
Title:
Optically induced charge-transfer in donor-acceptor-substituted p- and m- C2B10H12 carboranes
Contributor:
Wu, Lin;
Holzapfel, Marco;
Schmiedel, Alexander;
Peng, Fuwei;
Moos, Michael;
Mentzel, Paul;
Shi, Junqing;
Neubert, Thomas;
Bertermann, Rüdiger;
Finze, Maik;
Fox, Mark A.;
Lambert, Christoph;
Ji, Lei
imprint:
Springer Science and Business Media LLC, 2024
Published in:Nature Communications
Language:
English
DOI:
10.1038/s41467-024-47384-4
ISSN:
2041-1723
Origination:
Footnote:
Description:
<jats:title>Abstract</jats:title><jats:p>Icosahedral carboranes, C<jats:sub>2</jats:sub>B<jats:sub>10</jats:sub>H<jats:sub>12</jats:sub>, have long been considered to be aromatic but the extent of conjugation between these clusters and their substituents is still being debated. <jats:italic>m</jats:italic>- and <jats:italic>p</jats:italic>-Carboranes are compared with <jats:italic>m</jats:italic>- and <jats:italic>p</jats:italic>-phenylenes as conjugated bridges in optical functional chromophores with a donor and an acceptor as substituents here. The absorption and fluorescence data for both carboranes from experimental techniques (including femtosecond transient absorption, time-resolved fluorescence and broadband fluorescence upconversion) show that the absorption and emission processes involve strong intramolecular charge transfer between the donor and acceptor substituents via the carborane cluster. From quantum chemical calculations on these carborane systems, the charge transfer process depends on the relative torsional angles of the donor and acceptor groups where an overlap between the two frontier orbitals exists in the bridging carborane cluster.</jats:p>