Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 23, Issue 27, Pages 6682-6692Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201700759
Keywords
aromaticity; electrochemistry; expanded porphyrinoids; magnetic circular dichroism; porphyrinoids; protonation; photophysics
Categories
Funding
- U.S. National Science Foundation [CHE-1402004]
- Robert A. Welch Foundation
- Japan Society for the Promotion of Science (JSPS) [16K05700, 17H05377, JP15H02172, JP15H009]
- JSPS
- National Research Foundation (NRF) of South Africa
- Global Research Laboratory [2013K1A1A202050183]
- Basic Science Research Program [2015R1A2A1A10052586]
- Ministry of Science, ICT (Information and Communication Technologies) and Future Planning
- Grants-in-Aid for Scientific Research [16K05700, 17H05377, 15K05409] Funding Source: KAKEN
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1402004] Funding Source: National Science Foundation
Ask authors/readers for more resources
Detailed electronic, structural, photophysical, and redox studies of a series of meso-pentafluorophenyl-substituted hexaphyrins, namely amethyrin (1), rosarin (2), and rubyrin (3), are described. In prior work, it was found that the electronic states of the antiaromatic hexapyrrolic macrocycle, [24]rosarin 2, could be modified by exposure to several BrOnsted acids (e.g., HCl, HBr and HI) to produce either one- and two-electron reduced species, or both. In an effort to gain further insights into the reactivity of hexaphyrins possessing different -conjugation pathways, the -dodecamethyl-substituted [24]amethyrin 1 was prepared and its electronic structure was analyzed along with that of the o-phenylene-bridged [26]rubyrin 3 and rosarin 2 The [4n] and [4n+2] -conjugated formulations of 2 and 3, respectively, were inferred from steady-state, fs-transient absorption and two photon absorption measurements. Similar photophysical analyses lead to the conclusion that 1 is best considered as nonaromatic or weakly antiaromatic. Magnetic circular dichroism (MCD) spectroscopic analyses of hexaphyrins 1 and 3, as well as comparisons to 2, and theoretical perimeter MO diagram analyses provided support for the electronic assignments. In contrast to what was found for 2, simple protonation of 1 and 3 by halohydric acids did not induce an evident, redox-based change in the electronic structure of the macrocycle.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available