Pd-Catalysed Direct Arylation of Distyrylbenzene: Strong Dual-state Fluorescence and Electrochromism.

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 560 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 1500 nm when a positive potential of 1.0 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 0.98 s and 1.05 s.

A croconic acid-derived narrow band gap conjugated microporous polymer.

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 ∼1350 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.

Solid-state red-emissive (cyano)vinylene heteroaromatics via Pd-catalysed C-H homocoupling.

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.