Distinct Helical Molecular Orbitals through Conformational Lock

• Published in: Chemistry : a European journal Vol. 26; no. 72; pp. 17342 - 17349
• Main Authors: Ozcelik, Ani, Aranda, Daniel, Gil‐Guerrero, Sara, Pola‐Otero, Xaquín A., Talavera, Maria, Wang, Liangxuan, Behera, Santosh Kumar, Gierschner, Johannes, Peña‐Gallego, Ángeles, Santoro, Fabrizio, Pereira‐Cameselle, Raquel, Alonso‐Gómez, J. Lorenzo
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 23.12.2020; Wiley Subscription Services, Inc
• Subjects: alkynes; Alkynes - chemistry; Chemistry; Chemistry, Multidisciplinary; chiroptics; Conformation; helical molecular orbitals; Models, Molecular; Molecular Conformation; Molecular orbitals; Physical Sciences; Polyenes - chemistry; Science & Technology; spirobifluorenes; structure elucidation; helical molecular orbitals; ROTATION; chiroptics; MACROCYCLES; alkynes; ECD SPECTRA; structure elucidation; SCAFFOLDS; ALLENES; spirobifluorenes
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202002561

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. Helical Molecular Orbitals: Systems presenting helical molecular orbitals can be real. We have proposed the conformational lock of acetylenic structures as a strategy to achieve such systems. As a proof of concept, we have designed and synthetized cyclic acetylenic spirobifluorenes featuring distinct helical molecular orbitals and high stability.