Polypyridyl Ru(II)-derivatized polypropylacrylate polymer with a terminal water oxidation catalyst. Application of reversible addition-fragmentation chain transfer polymerization
Polypyridyl Ru(II)-derivatized polypropylacrylate polymer with a terminal water oxidation catalyst. Application of reversible addition-fragmentation chain transfer polymerization
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DOI：
10.1039/c5dt00287g
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发表时间：
2015-01-01
影响因子：
4
通讯作者：
Meye, Thomas J.
中科院分区：
文献类型：
--
作者：
Fang, Zhen;Ito, Akitaka;Meye, Thomas J.
采用可逆加成-断裂链转移聚合(RAFT)、点击反应和端基官能化的方法，合成了水氧化催化剂(WOC)封端的Ru(II)聚吡啶基衍生物聚丙烯酸酯。在碳酸亚丙酯的循环伏安图中，生色团的氧化发生在1.27V对NHE，而催化剂的Ru-III/II波发生在0.84V对NHE。在Ru(II)生色团的激发下，激发态能量迁移是通过-Ru-II*--&Gt；-Ru-II-，能量转移沿聚合物链跳跃，部分到达末端催化剂中心，在那里-Ru-II*--&Gt；-Ru-II-OH22+能量转移被Delta G(En)=-2100 cm(-1)所有利于。添加MV2+作为电子转移受体，将聚合物上的-Ru-II*-激发态氧化为Ru(III)，-Ru-II*-+Mv2+-&Gt；-Ru-III-+MV+，最终，催化剂通过点对点电子转移跃迁和氧化，-Ru-III-
A Ru(II) polypyridyl-derivatized polypropylacrylate end-capped with a water-oxidation-catalyst (WOC) has been synthesized by using reversible addition-fragmentation chain transfer polymerization (RAFT) followed by click reaction and end-group functionalization. In cyclic voltammograms in propylene carbonate, chromophore oxidation occurs at 1.27 V vs. NHE and the Ru-III/II wave for the catalyst at 0.84 V vs. NHE. Upon excitation of the Ru(II) chromophore, excited-state energy migration occurs by site-to-site, -Ru-II*- -> -Ru-II-, energy transfer hopping along the polymer chain, in part, reaching the terminal catalyst site where -Ru-II*- -> -Ru-II-OH22+ energy transfer is favored by Delta G(en) = -2100 cm(-1). Added MV2+ as an electron transfer acceptor oxidizes the -Ru-II*- excited state on the polymer to Ru(III), -Ru-II*- + MV2+ -> -Ru-III- + MV+, and ultimately, the catalyst, by site-to-site electron transfer hopping and oxidation, -Ru-III-