Electron transfer from photoexcited naphthalene-1,4:5,8-bis(dicarboximide) radical anion to Mn(bpy)(CO)3X and Re(bpy)(CO)3X CO2 reduction catalysts linked via a saturated methylene bridge
作者:Jose F. Martinez、Nathan T. La Porte、Michael R. Wasielewski
DOI:10.1016/j.jphotochem.2018.11.047
日期:2019.3
8-bis(dicarboximide) (NDI) radical anion donor to Mn(bpy)(CO)3Br or Re(bpy)(CO)3Cl CO2 reduction catalysts via a methylene bridge have been synthesized and studied by femtosecond transient visible, near-infrared and mid-infrared spectroscopy. The use of the methylene bridge to link NDI to the complexes does not affect the reduction potentials of the metal complexes. Selective photoexcitation of NDI•− to 2*NDI•−
通过萘1,4:5,8-双(二甲叉酰亚胺)(NDI)自由基阴离子供体与Mn(bpy)(CO)3 Br或Re(bpy)(CO)3 Cl CO 2还原催化剂连接的超分子系统飞秒瞬态可见光,近红外和中红外光谱已合成并研究了亚甲基桥。使用亚甲基桥将NDI连接到配合物上不会影响金属配合物的还原电位。NDI •-到2 * NDI •的选择性光激发导致Mn和Re络合物上的联吡啶(bpy)配体超快还原,从而形成Mn(I)(bpy •-)(CO)3 X和Re(I )(bpy •−)(CO)3 X分别具有接近1的量子产率。根据先前的电化学数据,Mn(I)(bpy •-)(CO)3 X的初始形成是出乎意料的,这表明Mn(I)中心比bpy配体以更正的电位还原。此外,发现Mn配合物中的正电子转移速率比Re络合物中的快,而Re络合物中的反向电子转移速率高于Mn络合物中的。