5,20-Bis(alpha-oligothienyl)-substituted [26] hexaphyrins possessingelectronic circuits strongly perturbed by meso-oligothienyl substituents

Collection with item attached
2015
Item details URL
http://open-repository.kisti.re.kr/cube/handle/open_repository/473445.do
DOI
10.1039/c4sc03394a
Title
5,20-Bis(alpha-oligothienyl)-substituted [26] hexaphyrins possessingelectronic circuits strongly perturbed by meso-oligothienyl substituents
Description
The work at Kyoto was supported by JSPS KAKENHI of Grant Numbers25220802 and 25620031. H.M. acknowledges a JSPS Fellowship for YoungScientists. The work at Yonsei was supported by Global ResearchLaboratory (GRL) Program (2013-81472) of the Ministry of Education,Science, and Technology (MEST) of Korea.
abstract
A series of [26] hexaphyrins(1.1.1.1.1.1) bearing two alpha-oligothienyl substituents at 5,20-positions have been synthesised and are shown to have a dumbbell hexaphyrin conformation, to which the alpha-oligothienyl groups are linked with small dihedral angles to form an acyclic helix-like conjugated network. While their distinct diatropic ring currents and four reversible reduction waves characteristic of aromatic [26] hexaphyrins indicate that the [26] hexaphyrin aromatic circuits are viable, the absorption spectra and excited state dynamics are significantly perturbed, which becomes increasingly evident with elongation of the oligothienyl substituents. DFT calculations of these hexaphyrins indicated that the LUMO and LUMO + 1 are localised on the hexaphyrin circuit and the HOMO and HOMO - 1 are spread over the acyclic helix-like conjugation network, which can explain the perturbed absorption spectra.
provenance
Made available in Cube on 2018-09-28T10:19:46Z (GMT). No. of bitstreams: 0
language
English
author
Mori, Hirotaka
Suzuki, Masaaki
Kim, Woojae
Lim, Jong Min
Kim, Dongho
Osuka, Atsuhiro
orcid
Suzuki, Masaaki/0000-0001-8843-5532; Mori, Hirotaka/0000-0002-8750-6367
accessioned
2018-09-28T10:19:46Z
available
2018-09-28T10:19:46Z
issued
2015
citation
CHEMICAL SCIENCE(6): 3
issn
2041-6520
uri
http://open-repository.kisti.re.kr/cube/handle/open_repository/473445.do
Funder
미래창조과학부
Funding Program
중견연구자지원
Project ID
1711016728
Jurisdiction
Rep.of Korea
Project Name
Ultrafast Excitation Transport Phenomena in Various Multichromophoric Architectures Using Time-and Space-resolved Spectroscopic Technologies
rights
openAccess
type
article


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