Synthesis and charge-transfer chemistry of La2@I h-C80/Sc3N@Ih-C80-zinc porphyrin conjugates: Impact of endohedral cluster

Feng L, Radhakrishnan SG, Mizorogi N, Slanina Z, Nikawa H, Tsuchiya T, Akasaka T, Nagase S, Martin N, Guldi DM (2011)

Publication Type: Journal article, Original article

Publication year: 2011

Journal

Journal of the American Chemical Society American Chemical Society

Original Authors: Feng L., Gayathri Radhakrishnan S., Mizorogi N., Slanina Z., Nikawa H., Tsuchiya T., Akasaka T., Nagase S., Martin N., Guldi D.M.

Publisher: American Chemical Society

Book Volume: 133

Pages Range: 7608-7618

Journal Issue: 19

DOI: 10.1021/ja202331r

Abstract

Two stable electron donor-acceptor conjugates, that is, 3 and 5b, employing La@I-C and ScN@I -C, on one hand, and zinc tetraphenylporphyrin, on the other hand, have been prepared via [1 + 2] cycloaddition reactions of a diazo precursor. Combined studies of crystallography and NMR suggest a common (6,6)-open addition pattern of 3 and 5b. Still, subtly different conformations, that is, a restricted and a comparatively more flexible topography, emerge for 3 and 5b, respectively. In line with this aforementioned difference are the electrochemical assays, which imply appreciably stronger I-C /ZnP interactions in 3 when compared to those in 5b. Density functional calculations reveal significant attractions between the two entities of these conjugates, as well as their separately localized HOMOs and LUMOs. The geometrical conformations and LUMO distributions of 3 and 5b, at our applied computational level, are slightly varied with their different endohedral clusters. The clusters also exert different impact on the excited state reactivity of the conjugates. For example, 3 undergoes, upon photoexcitation, a fast charge separation process and yields a radical ion pair, whose nature, namely, (La@C)-(ZnP) ) versus (La@C)- (ZnP)), varies with solvent polarity. 5b, on the other hand, afforded the same (ScN@C)-(ZnP) ) radical ion pair regardless of the solvent. © 2011 American Chemical Society.

Authors with CRIS profile

Dirk Michael Guldi Lehrstuhl für Physikalische Chemie I

Involved external institutions

University of Tsukuba / 筑波大学 JP Japan (JP) National Institute for Basic Biology / 基礎生物学研究所 JP Japan (JP) Universidad Complutense de Madrid (UCM) ES Spain (ES)

How to cite

APA:

Feng, L., Radhakrishnan, S.G., Mizorogi, N., Slanina, Z., Nikawa, H., Tsuchiya, T.,... Guldi, D.M. (2011). Synthesis and charge-transfer chemistry of La2@I h-C80/Sc3N@Ih-C80-zinc porphyrin conjugates: Impact of endohedral cluster. Journal of the American Chemical Society, 133(19), 7608-7618. https://doi.org/10.1021/ja202331r

MLA:

Feng, Lai, et al. "Synthesis and charge-transfer chemistry of La2@I h-C80/Sc3N@Ih-C80-zinc porphyrin conjugates: Impact of endohedral cluster." Journal of the American Chemical Society 133.19 (2011): 7608-7618.

BibTeX: Download