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Distinct Helical Molecular Orbitals through Conformational Lock **
Author(s) -
Ozcelik Ani,
Aranda Daniel,
GilGuerrero Sara,
PolaOtero Xaquín A.,
Talavera Maria,
Wang Liangxuan,
Behera Santosh Kumar,
Gierschner Johannes,
PeñaGallego Ángeles,
Santoro Fabrizio,
PereiraCameselle Raquel,
AlonsoGómez J. Lorenzo
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002561
Subject(s) - twist , molecular orbital , atomic orbital , terminal (telecommunication) , chemistry , physics , crystallography , molecule , computer science , quantum mechanics , geometry , mathematics , telecommunications , electron
Several theoretical studies have proposed strategies to generate helical molecular orbitals (Hel‐MOs) in [ n ]cumulenes and oligoynes. While chiral even‐[ n ] cumulenes feature Hel‐MOs, odd‐[ n ] cumulenes may also present them if the terminal groups lie in different planes. However, the proposed systems have been either experimentally unfeasible or resulted in opposite pseudo‐degenerated Hel‐MOs. We hereby demonstrate the introduction of a remarkable energy difference between helical orbitals of opposite twist by fixing the torsion angle between the terminal groups in butadiyne fragments. To experimentally lock the conformation of the terminal groups, we designed and synthesized cyclic architectures by combining acetylenes with chiral spirobifluorenes. The high stability of these systems with distinct helical orbitals allowed their isolation and full characterization. In our view, these results constitute a step further in the development of real systems presenting helical molecular orbitals.