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Cross-linkable fluorene-diphenylamine derivatives for electrochromic applications Silja Abraham, Gayathri Prabhu T. Ganesh, Sunil Varughese, Biswapriya Deb, and Joshy Joseph ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b08218 • Publication Date (Web): 23 Oct 2015 Downloaded from http://pubs.acs.org on October 25, 2015
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ACS Applied Materials & Interfaces
Cross-linkable fluorene-diphenylamine derivatives for electrochromic applications Silja Abraham,† Gayathri Prabhu T. Ganesh,† Sunil Varughese,† Biswapriya Deb,†, ‡ and Joshy Joseph*, †, ‡ †
Photosciences and Photonics Section, Chemical Sciences and Technology Division, CSIR-
National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram 695019, Kerala, India. E-mail:
[email protected] ‡
Academy of Scientific and Innovative Research (AcSIR), CSIR-NIIST Campus, Trivandrum,
India. KEYWORDS: electrochromism, cross-linkable small molecules, spectroelectrochemistry, triarylamine derivatives, Buchwald-Hartwig amination, electrochromic device.
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ABSTRACT: Multicolor electrochromic systems based on heat cross-linkable arylamine substituted fluorene derivatives, FD and FDOMe are reported. These derivatives with pendant vinyl groups have been synthesized by Buchwald-Hartwig amination reaction and were well characterized using various analytical and spectroscopic techniques such as NMR, ESI-MS and single crystal X-ray diffraction analysis. FD and FDOMe exhibited thermally activated crosslinking above their melting temperatures, which was confirmed through absorption, differential scanning calorimetry (DSC), FT-IR, and wide angle X-ray diffraction (WAXD) techniques. Cross-linked FD films (FD-X) on ITO showed two reversible redox peaks at 0.74 V and 0.91 V (vs Ag/AgCl) which correspond to the formation of radical cations and dications, respectively. The corresponding redox peaks were observed at 0.6 V and 0.8 V for cross-linked FDOMe films (FDOMe-X). Spectroelectrochemical studies of the electrochromic films on ITO revealed multicolor electrochromism of FD-X (colorless - yellow - dark cyan) and FDOMe-X (colorless brick red - blue) with a color contrast of ~44% at 485 nm for FD-X and ~63% at 500 nm for FDOMe-X and good switching stability between neutral and oxidized states (>300 cycles) with low switching voltages (< 0.9 V for first oxidation and
