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Verfasst von:Menning, Sebastian [VerfasserIn]   i
 Krämer, Maximilian [VerfasserIn]   i
 Rominger, Frank [VerfasserIn]   i
 Dreuw, Andreas [VerfasserIn]   i
 Bunz, Uwe H. F. [VerfasserIn]   i
Titel:Bridged tolanes
Titelzusatz:a twisted tale
Verf.angabe:Sebastian Menning, Maximilian Krämer, Andrew Duckworth, Frank Rominger, Andrew Beeby, Andreas Dreuw, and Uwe H. F. Bunz
Umfang:8 S.
Fussnoten:Gesehen am 11.12.2017
Titel Quelle:Enthalten in: The journal of organic chemistry
Jahr Quelle:2014
Band/Heft Quelle:79(2014), 14, S. 6571-6578
ISSN Quelle:1520-6904
Abstract:The rotational motion of tolanes along their acetylene axis is not fully understood. What happens to the optical and electronic properties if the tolane backbone is forced into a twisted conformation? Several tethers were investigated to obtain tolanophanes, fixing the torsion angle of the two phenyl rings. X-ray crystal structures revealed tether-specific torsion angles in the solid state. The absorption, emission, and excitation spectra were recorded. Twisted tethered tolane conformers showed blue-shifted absorption; emission spectra were all torsionally independent and identical. The tethered tolanes were embedded in a rigid matrix by freezing to 77 K; well-resolved emission spectra were recorded for planar tolanes, but for twisted systems unexpectedly long-lived phosphorescence was observed. How is this triplet emission explained? Quantum chemical calculations (TDDFT/cam-B3LYP/6-31G*) of the unsubstituted tolane showed that intersystem crossing (ISC) is favored with largespin-orbit coupling, which occurs when the molecular orbitals are orthogonal to each other; this is the case at the crossing of S1/T7. Also, a small energy difference between singlet and triplet states is required; we found that ISC can favorably take place at four crossings: S1/T6, S1/T7, S1/T8,9, S1/T10.
DOI:doi:10.1021/jo5010235
URL:Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.

Verlag: http://dx.doi.org/10.1021/jo5010235
 DOI: https://doi.org/10.1021/jo5010235
Datenträger:Online-Ressource
Sprache:eng
K10plus-PPN:1566208890
Verknüpfungen:→ Zeitschrift

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