Redox‐Active Chiroptical Switching in Mono‐ and Bis‐Iron Ethynylcarbo[6]helicenes Studied by Electronic and Vibrational Circular Dichroism and Resonance Raman Optical Activity. Issue 56 (14th September 2018)

• Record Type: Journal Article
• Authors: Shen, Chengshuo; Srebro‐Hooper, Monika; Weymuth, Thomas; Krausbeck, Florian; Navarrete, Juan T. López; Ramírez, Francisco J.; Nieto‐Ortega, Belén; Casado, Juan; Reiher, Markus; Autschbach, Jochen; Crassous, Jeanne
• Is Part Of: Chemistry. Volume 24:Issue 56(2018)
• Page Start: 15067
• Page End: 15079
• Publication Date: 2018-09-14
• Subjects: chirality -- circular dichroism -- density functional calculations -- helical structures -- redox chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201803069
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Introducing one or two alkynyl–iron moieties onto a carbo[6]helicene results in organometallic helicenes (2 a, b ) that display strong chiroptical activity combined with efficient redox‐triggered switching. The neutral and oxidized forms have been studied in detail by electronic and vibrational circular dichroism, as well as by Raman optical activity (ROA) spectroscopy. The experimental results were analyzed and spectra were assigned with the help of first‐principles calculations. In particular, a recently developed method for ROA calculations under resonance conditions has been used to study the intricate resonance effects on the ROA spectrum of mono‐iron ethynylhelicene2 a . Abstract : Ironing in kinks : Introducing one or two alkynyl–iron moieties onto a carbo[6]helicene results in organometallic helicenes that display strong chiroptical activity combined with efficient redox‐triggered switching (see figure). The chiroptical properties and redox‐switching activity of iron alkynylhelicenes determined experimentally and theoretically are reported.