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Chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media

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Main Authors: Fujiki, Michiya, Abd Jalil, Jalilah, Suzuki, Nozomu, Taguchi, Makoto, Wei, Zhang, Mohamed Mehawed, Abdellatif, Nomura, Kotohiro
Other Authors: jalilahjalil@unimap.edu.my
Format: Article
Language:English
Published: RSC Publishing 2013
Subjects:
Agglomeration
Chiral optofluidic
Circularly polarized light
Online Access:http://dspace.unimap.edu.my/xmlui/handle/123456789/26068
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spelling my.unimap-260682013-06-25T06:41:35Z Chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media Fujiki, Michiya Abd Jalil, Jalilah Suzuki, Nozomu Taguchi, Makoto Wei, Zhang Mohamed Mehawed, Abdellatif Nomura, Kotohiro jalilahjalil@unimap.edu.my Agglomeration Chiral optofluidic Circularly polarized light Link to publisher's homepage at http://pubs.rsc.org/ Here we report the first chiral optofluidic system that enables the emergence and enhancement of chiroptical signals of μm-sized polymer particles from achiral all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) during mirror-symmetry-breaking aggregation due to the optically active fluidic media consisting of (R)-limonene (1R) and (S)-limonene (1S), chloroform and methanol. These results were proven by refractive index (RI) and specific rotation (SR) of the media as well as circular dichroism (CD), optical rotatory dispersion (ORD), circular polarised luminescence (CPL), UV-vis and photoluminescence spectral characteristics of PFV. For comparison, a triple bond linker poly[(9,9-di-n-octylfluoren-2,7-diyl)-alt-yleneethynylene] (PFE) aggregate, which is an analogue of PFV, did not show any CD-signals in the π-π* transition. Gaussian 03 (TD-DFT, B3LYP, 3-21G basis set) calculations of PFV and PFE trimer models suggested that PFV is CD-/CPL-silent helix due to an equal proportion of P- and M-helices in a double-well with a small barrier height, conversely, that PFE is inherently optically inactive due to non-helix conformation in a single-well. Under optimised chiral optofluid with specific RI values of 1.38-1.39, the μm-sized PFV particles showed a great enhancement in Kuhn's dissymmetry amplitudes by ∼1500 times compared to the computed value in helical models of PFV; the g CD at 473 nm reached +0.078 (1S) and -0.104 (1R), and the g CPL at 474 nm attained +0.056 (1S) and -0.077 (1R), while maintaining a high quantum yield (Φ PL) of 75-88% with a short PL lifetime of ∼0.5 ns. For comparison, as for six π-conjugated molecular aggregates with/without H-H repulsions, including trans-stilbene and diphenylacetyelene, with the help of the 1R-/1S-based media, any detectable CD signals were not observed. These results led to the idea that optically active π-conjugated polymers carrying longer alkyl side groups in a double-well potential may be needed to efficiently generate the corresponding optically active aggregates in the chiral tersolvents. 2013-06-25T06:41:35Z 2013-06-25T06:41:35Z 2012-08-14 Article RSC Advances, vol. 2(16), 2012, pages 6663-6671 2046-2069 http://pubs.rsc.org/en/Content/ArticleLanding/2012/RA/c2ra20430d http://hdl.handle.net/123456789/26068 en RSC Publishing
institution Universiti Malaysia Perlis
building UniMAP Library
collection Institutional Repository
continent Asia
country Malaysia
content_provider Universiti Malaysia Perlis
content_source UniMAP Library Digital Repository
url_provider http://dspace.unimap.edu.my/
language English
topic Agglomeration
Chiral optofluidic
Circularly polarized light
spellingShingle Agglomeration
Chiral optofluidic
Circularly polarized light
Fujiki, Michiya
Abd Jalil, Jalilah
Suzuki, Nozomu
Taguchi, Makoto
Wei, Zhang
Mohamed Mehawed, Abdellatif
Nomura, Kotohiro
Chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media
description Link to publisher's homepage at http://pubs.rsc.org/
author2 jalilahjalil@unimap.edu.my
author_facet jalilahjalil@unimap.edu.my
Fujiki, Michiya
Abd Jalil, Jalilah
Suzuki, Nozomu
Taguchi, Makoto
Wei, Zhang
Mohamed Mehawed, Abdellatif
Nomura, Kotohiro
format Article
author Fujiki, Michiya
Abd Jalil, Jalilah
Suzuki, Nozomu
Taguchi, Makoto
Wei, Zhang
Mohamed Mehawed, Abdellatif
Nomura, Kotohiro
author_sort Fujiki, Michiya
title Chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media
title_short Chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media
title_full Chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media
title_fullStr Chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media
title_full_unstemmed Chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media
title_sort chiral optofluidics: gigantic circularly polarized light enhancement of all-trans-poly(9,9-di-n-octylfluorene-2,7-vinylene) during mirror-symmetry-breaking aggregation by optically tuning fluidic media
publisher RSC Publishing
publishDate 2013
url http://dspace.unimap.edu.my/xmlui/handle/123456789/26068
_version_ 1643794829471121408
score 13.209306

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