State Key Lab of Supramolecular Structure and Materials, Jilin University , Changchun, 130012, P. R. China.
College of Chemistry, Jilin University , Changchun, 130012, P. R. China.
ACS Appl Mater Interfaces. 2017 Jun 14;9(23):20196-20204. doi: 10.1021/acsami.7b03199. Epub 2017 May 31.
A biomimetic system on reversible bond-coupled electron transfer (BCET) has been proposed and investigated in a switchable Rh-N molecule with redox active subunits. We discover that energy barrier of C-N bond breaking is reduced dramatically to less than 1/7 (from 40.4 to 5.5 kcal/mol), and 1/3 of the oxidation potential is simultaneously lowered (from 0.67 to 0.43 V) with the oxidation of Rh-N. The concept, cation-coupled electron transfer (CCET), is highly recommended by analyzing existing proton coupled electron transfer (PCET) and metal coupled electron transfer (MCET) along with aforementioned BCET, which have same characteristic of transferring positive charges, such as proton, metal ion, and organic cation. Molecular switch can be controlled directly by electricity through BCET process. Solid electrochromic device was fabricated with extremely high coloration efficiency (720 cm/C), great reversibility (no degradation for 600 cycles), and quick respond time (30 ms).
提出并研究了一种基于可逆键偶联电子转移（BCET）的仿生体系，该体系在具有氧化还原活性亚基的可切换 Rh-N 分子中。我们发现，C-N 键断裂的能垒显著降低，不到 1/7（从 40.4 降至 5.5 kcal/mol），同时氧化 Rh-N 可使 1/3 的氧化电位降低（从 0.67 降至 0.43 V）。通过分析现有的质子偶联电子转移（PCET）和金属偶联电子转移（MCET）以及上述 BCET，提出了阳离子偶联电子转移（CCET）的概念，它们具有转移正电荷（如质子、金属离子和有机阳离子）的相同特征。通过 BCET 过程，可以直接用电来控制分子开关。制备了具有极高着色效率（720 cm/C）、极好的可逆性（600 次循环无降解）和快速响应时间（30 ms）的固态电致变色器件。
