[2.2]- and [3.3]Paracyclophane as Bridging Units in Organic Dyads for Visible-Light-Driven Dye-Sensitized Hydrogen Production
[2.2]- and [3.3]Paracyclophane as Bridging Units in Organic Dyads for Visible-Light-Driven Dye-Sensitized Hydrogen Production
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[2.2]-和[3.3]对环芳烷作为有机二元体中的桥接单元用于可见光驱动的染料敏化氢生产
DOI：
10.1002/chem.202200790
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Masahiko Shibahara
中科院分区：
文献类型：
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作者：
Motonori Watanabe;Yuka Ono;Tatsumi Ishihara;Yuan Jay Chang;Masahiko Shibahara
合成了以[2.2]-和[3.3]对环番(PCP)为桥联基团的新型供体-受体二元组分，并将其用于制备染料敏化制氢体系。所有合成的化合物都含有吩噻嗪和氰基丙烯酸/吡啶基丙烯腈两部分，分别作为电子供体和受体。虽然循环伏安测试表明所有合成的二元体都具有类似的给电子性质，但[2.2]PCP部分的最低吸收能低于[3.3]PCP部分，这是因为其苯环之间的距离较短，可以有效地驱动给体和受体生色团之间的电荷转移。在可见光(>；395 nm)下，负载二元体的光催化剂在0.5 M甘油水溶液中产生可检测到的氢气。由于所建议的激发光子数在产氢过程中起着关键作用，因此最佳的周转次数和光电流顺序与产氢率呈现相同的趋势。
Novel donor–acceptor dyads containing [2.2]‐ and [3.3]paracyclophane (PCP) as the bridging moiety were synthesized and used to effectively fabricate dye‐sensitized hydrogen production systems. All the prepared compounds had a phenothiazine and a cyanoacrylic acid/pyridinyl acrylonitrile moiety acting as an electron donor and acceptor, respectively. Although cyclic voltammetry measurements showed similar electron‐donating properties among all the synthesized dyads, the lowest absorption energy of the [2.2]PCP moiety was lower than that of the [3.3]PCP one; this was due to its shorter distance between benzene rings, which could effectively drive the charge transfer between the donor and acceptor chromophores. Under visible light (>395 nm), a dyad‐loaded photocatalyst in a 0.5 M aqueous glycerol solution generated detectable hydrogen gases. The optimal turnover number and photocurrent order exhibited the same trend as the hydrogen production rate since the suggested number of excited photons played a critical role in hydrogen production.