Architecture of supramolecular metal complexes for photocatalytic CO2 reduction III: Effects of length of alkyl chain connecting photosensitizer to catalyst
Architecture of supramolecular metal complexes for photocatalytic CO2 reduction III: Effects of length of alkyl chain connecting photosensitizer to catalyst
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DOI：
10.1016/j.jphotochem.2008.12.014
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发表时间：
2009-09-05
影响因子：
4.3
通讯作者：
Ishitani, Osamu
中科院分区：
文献类型：
--
作者：
Koike, Kazuhide;Naito, Sayoko;Ishitani, Osamu
新的Ru（Ⅱ）-Re（Ⅰ）双核配合物[{Ru（dmb）（2）}-LL-{Re（CO）（3）Cl}]（2+）（DMB= 4，4 '-二甲基-2，2'-联吡啶）与1，2-双（4 '-甲基-[2，2']联吡啶-4-基）-乙烷（MebpyC（2）H（4）Mebpy），1，4-bis（4 '-甲基[2，2']联吡啶-4-基）丁烷（MebpyC（4）H（8）Mebpy）和1，6-双（4 '-甲基-[2，2']联吡啶-4-基）-己烷合成了（MebpyC（6）H（12）Mebpy）桥联配体（LL），并研究了其光催化还原CO2的活性。最有效的光催化剂具有MebpyC（2）H（4）Mebpy作为桥配体，但在具有MebpyC（4）H（8）Mebpy和MebpyC（6）H（12）Mebpy的二联体之间没有观察到光催化活性的差异。只有MebpyC（2）H（4）Mebpy配体能与Ru和Re发生弱相互作用，而其它桥配体则不能与Ru和Re发生弱相互作用.这种相互作用诱导了二联体的（MLCT）-M-3激发态与MebpyC（2）H（4）Mebpy的更高的还原猝灭效率。BNAH，因此CO2还原的量子产率更高。(C)2008年爱思唯尔BY。All rights reserved.
New Ru(II)-Re(I) binuclear complexes [{Ru(dmb)(2)}-LL-{Re(CO)(3)Cl}](2+)(dmb=4,4'-dimethyl-2,2'-bipyridine) with 1,2-bis(4'-methyl-[2,2']bipyridinyl-4-yl)-ethane (MebpyC(2)H(4)Mebpy), 1,4-bis(4'-methyl[2,2']bipyridinyl-4-yl)-butane(MebpyC(4)H(8)Mebpy), and 1,6-bis(4'-methyl-[2,2']bipyridinyl-4-yl)-hexane (MebpyC(6)H(12)Mebpy) as bridge ligands (LL) have been synthesized, and their photocatalytic activity for CO2 reduction has been investigated. The most efficient photocatalyst had MebpyC(2)H(4)Mebpy as the bridge ligand, but no difference in photocatalysis was observed between the diads with MebpyC(4)H(8)Mebpy and MebpyC(6)H(12)Mebpy. Weak interaction between the Ru and Re sites was observed only through the MebpyC(2)H(4)Mebpy ligand but not through the other bridge ligands. This interaction induces a higher reductive quenching efficiency of the (MLCT)-M-3 excited state of the diad with MebpyC(2)H(4)Mebpy by the reductant. BNAH, and consequently the quantum yield of CO2 reduction is higher. (C) 2008 Elsevier BY. All rights reserved.