Journal of The Electrochemical Society, 164 (2) H49-H55 (2017) H49 0013-4651/2017/164(2)/H49/7/$33.00©The Electrochemical Society
Synthesis and Fluorescence Properties of Carbazole Based
Asymmetric Functionalized Star Shaped Polymer
Merve Guzel,aErhan Karatas,b,zand Metin Aka,z
aChemistry Department, Faculty of Art and Science, Pamukkale University, Denizli 20070, Turkey bChemistry Department, Faculty of Science, Selcuk University, Konya 42075, Turkey
A fluorescent group containing novel asymmetric functionalized star shaped derivative (TPC) of 2,4,6-trichloro-1,3,5-triazine con-taining 2-hydroxy carbazole and 1-pyrenemethylamine was designed, synthesized and characterized. Polymerization of TPC was achieved in acetonitrile/lithium perchlorate (ACN/LiClO4) solvent/electrolyte couple via electrochemical techniques. Electrochromic properties of the PTPC were investigated via spectroelectrochemistry, kinetic and colorimetry studies. Optoelectrochemical inves-tigation of PTPC displayed electronic transitions at 308, 460 and 780 nm which are correspond toπ-π∗transition, polaron, and bipolaron band formations, respectively. Moreover, electrochromic and fluorescence properties of PTPC were investigated. For the first time, this study reports the huge potential of asymmetric functionalized triazine compounds as electrochromic material. © 2016 The Electrochemical Society. [DOI:10.1149/2.0741702jes] All rights reserved.
Manuscript submitted November 7, 2016; revised manuscript received December 6, 2016. Published December 17, 2016.
For the past decade, remarkable interest in the synthesis and char-acterization of compounds containing the s-triazine1–4ring have been observed. Molecules having s-triazine as a core have been widely used in industry because of their unique semiconducting, photophysi-cal and electrochemiphotophysi-cal properties. These functional conducting poly-mers are still great attention because they are promising candidates for numerous advanced technological applications such as light emit-ting diodes, electrochromic devices,7–12solar cells,5,6and sensors.13–16 Star-shaped polymers17–19can be thought of as an assembly of multi-ple linear polymers, called arms, attached to a central core. They have potential processing benefits because of their unique architecture in comparison with linear analogues.20
Electron donors like 1,3,5-triazines21and carbazoles22with high electron mobility, photochemical and thermal stability are frequently used as hole transport materials for balanced charge injection. Ow-ing to electron donatOw-ing effect of carbazole units, carbazole con-taining dyes show excellent photoconductivity and relatively intense luminescence.23 Presence of carbazole groups in the core structure can be greatly enhanced the thermal stability of organic compounds. Utilization of carbazole containing conducting polymers with thermal stability are important in promising technological applications.24
For organic electronic,25 fluorescent molecular probe26,27 and sensor28,29 applications, pyrene derivatives have attracted important interest. Owing to study their fluorescence properties, synthesis of pyrenes bearing various substituents have significant attention.30,31 1-pyrenemethylamine and 2,4,6-trichloro-1,3,5-triazine were selected to combine optical and electrical properties of triazine and pyrene.
A symmetric triazine (all 1,3,5 position of the triazine contain the same group) unit is a widely used building block for constructing ideal electron-transporting materials, host materials and emitters in OLEDs. In comparison with a symmetric triazine unit, an asymmetric triazine group has never in used as electrochromic material and has rarely been utilized as organic optoelectronic materials, especially as the emissive materials for OLEDs.
This work is focused on the investigation and application of newly synthesized asymmetric functionalized star shaped compound with the central 1,3,5-triazine ring. Electrochemical polymerization of PTPC was achieved by electrochemical polymerization in ace-tonitrile/lithium perchlorate solvent/electrolyte couple. While TPC is creamy-white color in solid state under UV-off, it is efficient blue emis-sion in solid state under UV-on. Moreover, TPC emits light-blue color in ACN solution. Optoelectrochemical and electrochromic properties of PTPC were investigated. PTPC showed electrochromism through almost the entire visible region, displaying transparent and green color with different applied potential. This novel material can be also used in OLED and solar cell applications.
zE-mail:erhankaratas@gmail.com;metinak@pau.edu.tr
Materials and Methods
Materials.—All of the reagents and solvents were used in this study; acetone (Aldrich), 2-hydroxy carbazole (Aldrich), 1-pyrenemethylamine hydrochloride (Aldrich), lithium perchlorate (Aldrich), sodium hydrogen carbonate (Aldrich), sodium hydroxide (Aldrich) were used as received from their indicated commercial suppliers without any further purification only just 2,4,6-trichloro-1,3,5-triazine (Merck) was purified by recrystallizations from pure petroleum ether (60–90◦C) and acetonitrile (Aldrich) was dried with using P2O5.
Instrumentations.—1H NMR spectra were recorded by the
Var-ian, 400-MHz Spectrometer at room temperature. FT-IR spectra were recorded using a Perkin Elmer Spectrum 100 with Universal ATR Polarization Accessory. Elemental analyses were carried out using a LECO-CHNS-932 elemental analyzers. Melting points were deter-mined by Stuart Melting Point Apparatus SMP30 instrument. Elec-tropolymerization and electrochemical measurements were carried out with an Ivium potentiostat/galvanostand an Agilent 8453 UV– vis spectrophotometer was used in order to perform the spectroelec-trochemical studies of the polymer. No background correction was done for all electrochemical measurements. Colorimetry measure-ments were made with a Minolta CS-100 spectrophotometer.
Synthesis of 4,6-dichloro-2-pyrenemethylamine-1,3,5-triazine (TP).—To a solution of 2,4,6-trichloro-1,3,5-triazine (0.184 g, 1× 10−3mol) in acetone 10 mL at 0–5◦C was added 5 mL aqueous so-lution of NaHCO3(0.084 g, 1× 10−3mol). When the mixture was
like a slurry, was added 1-pyrenemethylamine hydrochloride (0.267 g, 1× 10−3mol) and NaHCO3(0.084 g, 1× 10−3mol) in 30 mL
ace-tone/water (2:1 v/v). To maintain the pH between 6.0 and 7.0 during the reaction, small amount of NaHCO3was added to this mixture. The
mixture was allowed to stirr at 0–5◦C for 4 h, then 15 mL cold water was added to the mixture and precipitated was filtered. The precipitate as yellow powder was washed with water and a small amount of cold acetone. Its melting point was 190◦C. Synthesis route of product is shown schematically in Scheme1. Elemental analysis; %Calculated (Found): C 63.34 (63.82), H 3.19 (3.42), N 14.77 (15.18).
Synthesis of 4,6-bis(9H-carbazol-2-yloxy)-2-(pyrenemethy lamine)-1,3,5 triazine (TPC).—4,6-dichloro-2-pyrenemethylamine-1,3,5-triazine (0.189 g, 0.5× 10−3mol) was dissolved in acetone (15 ml) and a solution of 2-hydroxycarbazole (0.183 g, 1× 10−3 mol) and NaOH (0.04 g, 1× 10−3 mol) in 5 ml Acetone/Water (4:1v/v) was added dropwise. The reaction mixture was stirred vigorously under N2for 1 h at between 0 and 5◦C and then at room temperature
for 4 h., finally under reflux overnight. The reaction mixture was then cooled to 0◦C. A creamy white crystalline solid was filtered. The precipitate was washed with cold water and small amount of
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