RESUMEN
Given the rapid growth of the nuclear sector, effective treatment of radioactive iodine is critical. Herein, we report the synthesis and the iodine adsorption properties of croconic acid (CTPB) and squaric acid (STPB) containing π-conjugated novel zwitterionic conjugated porous polymers (CPPs). The CPPs have been synthesized through a condensation reaction of tris(4-aminophenyl)benzene with croconic acid or squaric acid in high yields (~95%). The ionic nature of the polymers promoted high iodine/polyiodide vapour adsorption capacity of up to 4.6 g/g for CTPB and 3.5 g/g for STPB under ambient pressure at 80 °C. The zwitterionic framework (croconic acid or squaric acid units) coupled with the aromatic units is expected to effectively capture molecular iodine (I2) and polyiodides (I3- and I5-). The iodine adsorption properties of the polymers have been studied using Fourier-Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Brauner-Emmett-Teller (BET) analysis, and Raman Spectroscopy. Besides this work, there are only three ionic units for effective iodine adsorption. This work demonstrates the importance of zwitterionic units in the porous network reported for iodine adsorption and separation.
RESUMEN
Distyrylbenzenes (DSBs) are well-known for their strong multicolour fluorescence. Fluorescence tuning of DSB via further functionalization/arylation, on the other hand, is uncommon. This paper reports a Pd-catalysed direct arylation approach for introducing different aryl groups onto fluorobenzene-containing DSB moiety (7) in high yields (67-72 %). The versatile methodology allows the substitution of neutral [tolyl (1)], electron-deficient [p-formyl benzene (2), p-acetyl benzene (3), p-nitrobenzene (4)] and electron-rich [carbazole (5), triphenylamine (6)] aryl groups. The electron-deficient aryls render mono-substitution, while the electron-rich counterparts promote di-substitution. The compounds (1-6) show blue, green, and yellow fluorescence in both the solution and solid states; the fluorescence quantum yields reach >98 % and the peak maxima span from 425 to 560â nm. The mono-carbazole DSB (5) exhibit white light emission (WLM) in polar solvents (acetone, DMF, CH3CN, DMSO and NMP) with very high fluorescence quantum yields (φf) of 60-80 %. For WLM, such high efficiency (φf) is somewhat uncommon. Moreover, visible-to-NIR reversible electrochromism is demonstrated by the TPA-integrated DSB (6). The colour of 6 changes from pristine light yellow to orange, and the absorption maxima shifts from 372 to 1500â nm when a positive potential of 1.0â V vs Ag/Ag+ is applied. Moreover, the system shows high colouration efficiency in the NIR region with fast switching speeds for colouration and decolouration as fast as 0.98â s and 1.05â s.
RESUMEN
Croconic acid, a novel highly electron-deficient building block, was introduced into a conjugated microporous polymer (CTPA). The CMP possesses strong donor-acceptor interactions, which resulted in near-IR absorption (red edge â¼1350 nm), a narrow bandgap (<1 eV) and high electrical conductivity upon doping (0.1 S m-1). Compared to the squaric acid congener (STPA), CTPA showed superior optical, electronic and electrical properties.
Asunto(s)
Electrónica , Electrones , Conductividad Eléctrica , PolímerosRESUMEN
Thiophene-based π-conjugated systems are important materials for organic electronics; thus, their synthesis is of topical interest. We report fluorescent thiophene/furan-based vinylene and cyanovinylene systems via Pd-catalysed homocoupling [Pd(OAc)2, pivalic acid, KOAc, DMAc, 140 °C]. The methodology is versatile and allows the development of a variety of π-conjugated systems without the need for pre-functionalized building units. The reaction tolerates electron-rich, electron-deficient and large π-conjugated substrates. The developed compounds absorb in the visible region (400-515 nm) and emit green to orange fluorescence in the solution state (510-600 nm). Most importantly, the compounds exhibit strong aggregation-induced emission (AIE) in the NIR region (λem = 650 nm), with quantum yields reaching up to 10%. Steric hindrance imparted by vinylene/cyanovinylene units is responsible for the strong solid-state luminescence. DFT-optimized structures reveal an apparent twist of 20-40° in the molecular backbone of the compounds, supporting the AIE behaviour of the compounds.