Ye Ya-Ling, Pan Kai-Yun, Ni Bi-Lian, Sun Wei-Ming
Fujian Key Laboratory of Drug Target Discovery and Structural and Functional Research, The School of Pharmacy, Fujian Medical University, Fuzhou, China.
School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, China.
Front Chem. 2022 Mar 14;10:853160. doi: 10.3389/fchem.2022.853160. eCollection 2022.
In this study, to examine the possibility of using cage-like complexants to design nonmetallic superalkalis, a series of X@3adz (X = H, B, C, N, O, F, and Si) complexes have been constructed and investigated by embedding nonmetallic atoms into the 3adamanzane (3adz) complexant. Although X atoms possess very high ionization energies, these resulting X@3adz complexes possess low adiabatic ionization energies (AIEs) of 0.78-5.28 eV. In particular, the adiabatic ionization energies (AIEs) of X@3adz (X = H, B, C, N, and Si) are even lower than the ionization energy (3.89 eV) of Cs atoms, and thus, can be classified as novel nonmetallic superalkalis. Moreover, due to the existence of diffuse excess electrons in B@3adz, this complex not only possesses pretty low AIE of 2.16 eV but also exhibits a remarkably large first hyperpolarizability ( ) of 1.35 × 10 au, indicating that it can also be considered as a new kind of nonlinear optical molecule. As a result, this study provides an effective approach to achieve new metal-free species with an excellent reducing capability by utilizing the cage-like organic complexants as building blocks.
在本研究中，为了探究使用笼状络合剂设计非金属超碱的可能性，通过将非金属原子嵌入3 - 金刚烷（3adz）络合剂中，构建并研究了一系列X@3adz（X = H、B、C、N、O、F和Si）络合物。尽管X原子具有非常高的电离能，但这些生成的X@3adz络合物具有0.78 - 5.28电子伏特的低绝热电离能（AIEs）。特别地，X@3adz（X = H、B、C、N和Si）的绝热电离能（AIEs）甚至低于Cs原子的电离能（3.89电子伏特），因此，可以归类为新型非金属超碱。此外，由于B@3adz中存在弥散的多余电子，该络合物不仅具有相当低的2.16电子伏特的AIE，而且表现出1.35×10 au的非常大的第一超极化率（ ），表明它也可以被视为一种新型非线性光学分子。因此，本研究提供了一种有效的方法，通过利用笼状有机络合剂作为构建单元来实现具有优异还原能力的新型无金属物种。
