A tethered tolane

• Verfasst von: Kozhemyakin, Yury [VerfasserIn]
• Verfasst von: Krämer, Maximilian [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Verfasst von: Bunz, Uwe H. F. [VerfasserIn]
• Titel: A tethered tolane
• Titelzusatz: twisting the excited state
• Verf.angabe: Yury Kozhemyakin, Maximilian Krämer, Frank Rominger, Andreas Dreuw, and Uwe H. F. Bunz
• E-Jahr: 2018
• Jahr: 13 August 2018
• Umfang: 4 S.
• Fussnoten: Version of record online: September 11, 2018 ; Gesehen am 30.01.2020
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2018
• Band/Heft Quelle: 24(2018), 57, Seite 15219-15222
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201804095
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: bridged chromophores
• Sach-SW: tolane
• Sach-SW: tolanophane
• Sach-SW: twisting
• K10plus-PPN: 168890963X

Abstract

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.