Great attention has been paid to cofacial porphyrins due to their many unique advantages over their monomeric analogs.However,their synthesis is usually complicated.In this work,a facile impregnation method for prepar...Great attention has been paid to cofacial porphyrins due to their many unique advantages over their monomeric analogs.However,their synthesis is usually complicated.In this work,a facile impregnation method for preparing heterogenized,cofacially stacked porphyrins is proposed.An anionic porphyrin is introduced as an underlayer for immobilization of cationic cobalt porphyrin via electrostatic force.The metal center of the underlying molecule contributes to the electronic structure of the upper cationic cobalt porphyrin.Screening reveals the anionic iron porphyrin to be the most efficient underlayer molecule,lowering the activation energy barrier of CO_(2) electroreduction,with an improved turnover frequency by 74%to8.0 s~(-1)at-0.6 V versus RHE.展开更多
A novel mixed-trib ridged dimolybdenum(Ⅰ) compound [Bu4N][Mo2(n-SPh)2(u-Cl)(CO)6] (1) has been synthesized from the reaction of Mo2 (CO)8 (SPh)2 with ButNCl.Compound 1 was characterized by IR,UV-Vis and 1H,13C,95Mo N...A novel mixed-trib ridged dimolybdenum(Ⅰ) compound [Bu4N][Mo2(n-SPh)2(u-Cl)(CO)6] (1) has been synthesized from the reaction of Mo2 (CO)8 (SPh)2 with ButNCl.Compound 1 was characterized by IR,UV-Vis and 1H,13C,95Mo NMR spectroscopic analyses.The electrochemical behavior was measured by cyclic voltammetry,indicating a quasi-reversible two-electron transfer in one step.The crystal structure determined by X-ray crystallography shows that 1 contains a [Mo2(u-S)2(u-Cl)]- core with a planar Mo2S2 unit and a Cl bridge.The Mo-Mo distance is 0.28709(7) nm,and the Mo-Cl-Mo angle is 66.44(4).A newface-sharing bioctahedral structure is discussed.展开更多
基金sponsored by the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning and Shanghai Sailing Program(No.19YF1410600)the Young Scientists Fund of the National Natural Science Foundation of China(No.21905240)the State Key Laboratory of Marine Pollution(SKLMP)Seed Collaborative Research Fund。
文摘Great attention has been paid to cofacial porphyrins due to their many unique advantages over their monomeric analogs.However,their synthesis is usually complicated.In this work,a facile impregnation method for preparing heterogenized,cofacially stacked porphyrins is proposed.An anionic porphyrin is introduced as an underlayer for immobilization of cationic cobalt porphyrin via electrostatic force.The metal center of the underlying molecule contributes to the electronic structure of the upper cationic cobalt porphyrin.Screening reveals the anionic iron porphyrin to be the most efficient underlayer molecule,lowering the activation energy barrier of CO_(2) electroreduction,with an improved turnover frequency by 74%to8.0 s~(-1)at-0.6 V versus RHE.
基金Project supported by the National Natural Science Foundation of China (No. 29733090-3)State Key Laboratory of Stractural Chemistry (No. 980008)
文摘A novel mixed-trib ridged dimolybdenum(Ⅰ) compound [Bu4N][Mo2(n-SPh)2(u-Cl)(CO)6] (1) has been synthesized from the reaction of Mo2 (CO)8 (SPh)2 with ButNCl.Compound 1 was characterized by IR,UV-Vis and 1H,13C,95Mo NMR spectroscopic analyses.The electrochemical behavior was measured by cyclic voltammetry,indicating a quasi-reversible two-electron transfer in one step.The crystal structure determined by X-ray crystallography shows that 1 contains a [Mo2(u-S)2(u-Cl)]- core with a planar Mo2S2 unit and a Cl bridge.The Mo-Mo distance is 0.28709(7) nm,and the Mo-Cl-Mo angle is 66.44(4).A newface-sharing bioctahedral structure is discussed.
