在2.1V范围内调节亚铁氰化物的形式电位。

McNicholas Brendon J, Grubbs Robert H, Winkler Jay R, Gray Harry B, Despagnet-Ayoub Emmanuelle

Beckman Institute , Division of Chemistry and Chemical Engineering , California Institute of Technology , 1200 East California Boulevard, Mail Code 139-74 , Pasadena , California 91125 , USA . Email:

Occidental College , Norris Hall of Chemistry , 1600 Campus Rd , Los Angeles , CA 90041 , USA.

Chem Sci. 2019 Feb 21;10(12):3623-3626. doi: 10.1039/c8sc04972f. eCollection 2019 Mar 28.

We report the synthesis and characterization of homoleptic borane adducts of hexacyanoferrate(ii). Borane coordination blueshifts d-d transitions and CN IR and Raman frequencies. Control over redox properties is established with respect to borane Lewis acidity, reflected in peak anodic potential shifts per borane of +250 mV for BPh and +350 mV for B(CF). Electron transfer from [Fe(CN-B(CF))] to photogenerated [Ru(2,2'-bipyridine)] is very rapid, consistent with voltammetry data. Coordination by Lewis acids provides an avenue for selective modification of the electronic structures and electrochemical properties of cyanometalates.

我们报道了六氰合铁（II）酸盐的同配体硼烷加合物的合成与表征。硼烷配位使d-d跃迁以及CN的红外和拉曼频率发生蓝移。相对于硼烷路易斯酸度建立了对氧化还原性质的控制，这体现在每个硼烷的峰值阳极电位偏移上，对于BPh为+250 mV，对于B(CF)为+350 mV。从[Fe(CN-B(CF))]到光生[Ru(2,2'-联吡啶)]的电子转移非常迅速，这与伏安法数据一致。路易斯酸配位为选择性修饰氰基金属配合物的电子结构和电化学性质提供了一条途径。