Trans/cis-isomerization of fluorene-bridged azo chromophore with significant two-photon absorbability at near-infrared wavelength

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题名:	Trans/cis-isomerization of fluorene-bridged azo chromophore with significant two-photon absorbability at near-infrared wavelength
作者:	林子超;Chu, Chih-Chien;Chang, Ya-Chi;Tsai, Bo-Kai;Lin, Tzu-Chau;Lin, Ja-Hon;Hsiao, Vincent K. S.
贡献者:	理學院化學學系
关键词:	absorption;azo compounds;Azo Compounds - chemical synthesis;Azo Compounds - chemistry;charge transfer;Chemistry;Chromatography, High Pressure Liquid;chromophores;Fluorine - chemistry;isomerization;Magnetic Resonance Spectroscopy;Molecular Structure;Photons;Quantum Theory;Spectrophotometry, Ultraviolet;Spectroscopy, Near-Infrared;Spectrum Analysis, Raman;Stereoisomerism
日期:	2014-01-01
上传时间:	2026-04-21 14:22:44 (UTC+8)
出版者:	John Wiley and Sons Ltd;Weinheim: WILEY-VCH Verlag
摘要:	摘要： Azo‐containing materials have been proven to possess second‐order nonlinear optical (NLO) properties, but their third‐order NLO properties, which involves two‐photon absorption (2PA), has rarely been reported. In this study, we demonstrate a significant 2PA behavior of the novel azo chromophore incorporated with bilateral diphenylaminofluorenes (DPAFs) as a π framework. The electron‐donating DPAF moieties cause a redshifted π–π* absorption band centered at 470 nm, thus allowing efficient blue‐light‐induced trans‐to‐cis photoisomerization with a rate constant of 2.04×10−1 min−1 at the photostationary state (PSS). The open‐aperture Z‐scan technique that adopted a femtosecond (fs) pulse laser as excitation source shows an appreciably higher 2PA cross‐section for the fluorene‐derived azo chromophore than that for common azobenzene dyes at near‐infrared wavelength (λex=800 nm). Furthermore, the fs 2PA response is quite uniform regardless of the molecular geometry. On the basis of the computational modeling, the intramolecular charge‐transfer (ICT) process from peripheral diphenylamines to the central azo group through a fluorene π bridge is crucial to this remarkable 2PA behavior. Light absorber: A fluorene‐bridged azo chromophore shows an intense π–π* absorption in the blue‐light region, thus allowing a trans‐to‐cis photoisomerization under blue light‐emitting diode (LED) excitation (see scheme). The azo material also has significant two‐photon absorption in the near‐IR wavelength under the excitation of a femtosecond pulse laser beam. 其他題名： Chem. Asian J 出版者： Weinheim: WILEY-VCH Verlag 出版日期： 2014-12 出處： Chemistry, an Asian journal, 2014-12, Vol.9 (12), p.3390-3396 版權： 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim 版權： 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. 版權： 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 識別號： ISSN: 1861-4728 識別號： ISSN: 1861-471X 識別號： EISSN: 1861-471X 識別號： DOI: 10.1002/asia.201402896 識別號： PMID: 25294108
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