A tethered tolane: twisting the excited state

The synthesis of a doubly bridged tolane is reported. The target is obtained in a five-step synthesis, starting from commercially available 2-amino-meta-xylene by a combination of a Sandmeyer reaction, radical bromination, and Stille-type coupling, followed by double ring closing. The doubly tethere...

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Bibliographic Details
Main Authors: Kozhemyakin, Yury (Author) , Krämer, Maximilian (Author) , Rominger, Frank (Author) , Dreuw, Andreas (Author) , Bunz, Uwe H. F. (Author)
Format: Article (Journal)
Language:English
Published: 13 August 2018
In: Chemistry - a European journal
Year: 2018, Volume: 24, Issue: 57, Pages: 15219-15222
ISSN:1521-3765
DOI:10.1002/chem.201804095
Online Access:Resolving-System, Volltext: https://doi.org/10.1002/chem.201804095
Verlag: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201804095
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Author Notes:Yury Kozhemyakin, Maximilian Krämer, Frank Rominger, Andreas Dreuw, and Uwe H. F. Bunz
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Summary:The synthesis of a doubly bridged tolane is reported. The target is obtained in a five-step synthesis, starting from commercially available 2-amino-meta-xylene by a combination of a Sandmeyer reaction, radical bromination, and Stille-type coupling, followed by double ring closing. The doubly tethered tolane is crystalline; the two phenyl rings are highly twisted with respect to each other both in solution and in the solid state. Optical spectroscopy and quantum chemical calculations show that the doubly bridged tolane is twisted not only in the ground state, but also in the excited state, leading to emission from the twisted state in solution and in the solid state. Strong phosphorescence is observed at cryogenic temperatures.
Item Description:Version of record online: September 11, 2018
Gesehen am 30.01.2020
Physical Description:Online Resource
ISSN:1521-3765
DOI:10.1002/chem.201804095