Enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate mediated by a self-assembled iron tetrahedral coordination cage

• Published in: Journal of photochemistry and photobiology. A, Chemistry. Vol. 331; pp. 95 - 101
• Main Authors: Alagesan, Mani, Kanagaraj, Kuppusamy, Wan, Shigang, Sun, Huiqin, Su, Dan, Zhong, Zhihui, Zhou, Dayang, Wu, Wanhua, Gao, Guowei, Zhang, Hui, Yang, Cheng
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01.12.2016; Elsevier BV
• Subjects: Anthracene; Cages; Chirality; Circular dichroism; Cooordination cage; Dichroism; Enantiomers; Iron; Molecular chemistry; NMR; Nuclear magnetic resonance; Photochemistry; Photocyclodimerization; Self-assembly; Studies; Supramolecular compounds; Temperature effect; Temperature effects; Temperature effect; Photocyclodimerization; Anthracene; Cooordination cage; Chirality
• ISSN: 1010-6030; 1873-2666
• DOI: 10.1016/j.jphotochem.2015.10.023

[Display omitted] •An enantiopure molecular cage was used for mediating a chiral photodimerization.•The intrinsically chiral cage demonstrated efficiency in the chiral induction.•External factors play a remarkable role in the supramolecular photochirogenesis. Photochirogenesis through supramolecular assembly provides an intriguing approach to the highly challenging research field of chiral photochemistry. In the present paper, an enantiopure coordination self-assembly cage (cage T) has been employed for mediating the enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylate (AC) in aqueous medium. The complexing behavior of AC with the cage T has been investigated by UV–vis, circular dichroism and NMR spectral studies. It was found that in aqueous solution, cage T could form both 1:1 and 1:2 host–guest complexes with AC. Photocyclodimerization of AC mediated by cage T were studied at different temperatures and different host/guest ratios. The anti-HT photodimer dominate the photocyclodimerization of AC with cage T. In the presence of an enantiopure cage T, the chiral syn-HT and anti-HH photodimers were produced in moderate enantioselectivity. The enantiodifferentiating mechanism of this supramolecular photochirogenesis system and the effects of external factors are discussed.