Two novel water-soluble π-conjugated small molecules based on dibenzothiophene-S,S-dioxide and bispyridinium salts, named FSOPyCl and FSOmiCl, were successfully synthesized. Both molecules showed deep blue light emission, with photoluminescence peaks at about 408 and 405 nm in aqueous solution, respectively. Their photoluminescence quantum yields (PLQYs) in aqueous solution were as high as 68.9% and 50.3%, respectively. Electrochemical measurements suggested that they have excellent electron affinity, with lowest unoccupied molecular orbital (LUMO) energy levels at −3.78 and −3.94 eV, respectively. Due to their unique properties including large planarity, good thermal stability, excellent electron affinity and high fluorescence efficiency, FSOPyCl and FSOmiCl may be promising construction units for preparing water/alcohol-soluble conjugated materials with good optoelectronic performance.
A novel n-type cationic conjugated polymer ( PFSOmiCl ), consisting of bispyrimidinium-dibenzothiophene- S , S -dioxide and fluorene scaffolds, was developed from its polymeric precursor ( PFSOmi ) through an intramolecular cyclization reaction . In comparison with PFSOmi , PFSOmiCl exhibits significant bathochromical absorption and photoluminescence spectra in both solution and film form, as well as a more hydrophilic film surface. Cyclic voltammetry tests demonstrate that PFSOmiCl possesses a deep lowest unoccupied molecular orbital (LUMO) energy level of −4.18 eV, which is comparable to the LUMO energy levels of common fullerene derivatives. These unique properties endow PFSOmiCl with great utilization potential in organic optoelectronic devices. Moreover, this research offers a novel guideline for designing new conjugated polyelectrolytes .
Ge Shu,Yuda Li,Zhuang Wang,Jia-Xing Jiang,Feng Wang
Conjugated polymers have recently emerged as encouraging metal-free photocatalysts for solar energy conversion under visible light irradiation. Unfortunately, photocatalytic activities of the current polymers are still inadequate. Herein, we present a simple but quite attractive conjugated homopolymer (PDBTSO) based a dibenzothiophene-S,S-dioxide moiety. The introduction of sulphonyl group to a polyfluorene-like backbone can cause richly available active sites and lead to the efficient separation of photoexcited charge carriers, thus yielding impressive photocatalytic performance. Furthermore, we explored a natural “phosphorylation” strategy for increasing photocatalytic hydrogen production over PDBTSO. Remarkably, an extremely high hydrogen evolution rate of 44.2 mmol h −1 g −1 was achieved with the optimum addition of K 2 HPO 4 under visible light irradiation.
Photocatalytic conversion of benzyl alcohol (BA) into value-added fine chemicals and hydrogen (H 2 ) in water medium provides a novel strategy for green synthesis. The construction of Z-scheme heterostructures not only realize enhanced charge-separation efficiency, but also remain strong drive force for photocatalytic reaction, which exhibit great potentials toward simultaneously generating benzaldehyde (BAD) and H 2 . Herein, we report a noble-metal-free Z-scheme photocatalytic system consisting poly(dibenzothiophene-S,S-dioxide) (PSO) and α-Fe 2 O 3 for selective oxidation of BA with synchronous H 2 production. Such nanocomposites can effectively transfer and reduce the recombination of photoexcited charge carriers, therefore maintaining the oxidizability of holes of α-Fe 2 O 3 and the reducibility of electrons of PSO. As expected, PSO-Fe 2 O 3 with a mass of ∼5 mg under optimal composition ratio exhibited an impressive photocatalytic activity with BAD and H 2 yields up to 23.1 and 29.5 μmol h −1 , respectively, which is among the top photocatalytic performance reported so far for selective photocatalytic oxidation of BA in the aqueous solution.
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