Controlling the spin state of diphenylcarbene via halogen bonding: A theoretical study
文献类型：期刊论文
| 作者 | Ge, Yang1; Lu, Yunxiang1; Xu, Zhijian2 ; Liu, Honglai1
|
| 刊名 | INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
 |
| 出版日期 | 2018-08-05 |
| 卷号 | 118期号:15 |
| 关键词 | diphenylcarbene halogen bonding minimum energy crossing point spin flip |
| ISSN号 | 0020-7608 |
| DOI | 10.1002/qua.25616 |
| 文献子类 | Article |
| 英文摘要 | Halogen bonding has recently become an effective tool to control the spin state of reactive carbenes. In this work, a series of the complexes of diphenylcarbene (DPC) that has a triplet ground state with several halogen bond donors RX were theoretically studied, and in particular, the influence of the formation of halogen bonding on the spin state of DPC was extensively explored. The spin flip depends on the difference of halogen bond energies between triplet and singlet, that is, when the difference is large enough a spin flip may occur. Furthermore, the variations of the geometries on complexation may induce the potential energy surfaces of different spin states to intersect, thus leading to intersystem crossing. Based on the energy analysis of the minimum energy crossing points (MECPs), the systems with a smaller MECP-triplet energy barrier go through intersystem crossing more easily. Halogen bonds in the complexes, where a spin flip takes place, exhibit a partially covalent character, while other complexes show conventional behaviors of halogen bonding. According to charge decomposition analysis, the charge transfer from HOMO (DPC) to LUMO (RX) is identified as a prominent stabilizing interaction in the whole complexes. |
| WOS关键词 | SUPRAMOLECULAR CHEMISTRY ; HYDROGEN-BONDS ; CARBENE ; TRIPLET ; SINGLET ; COMPLEXES ; DYNAMICS ; DONOR |
| 资助项目 | National Natural Science Foundation of China[21473054] |
| WOS研究方向 | Chemistry ; Mathematics ; Physics |
| 语种 | 英语 |
| WOS记录号 | WOS:000438343200011 |
| 出版者 | WILEY |
| 源URL | [http://119.78.100.183/handle/2S10ELR8/279626]  |
| 专题 | 药物发现与设计中心 |
| 通讯作者 | Lu, Yunxiang |
| 作者单位 | 1.East China Univ Sci & Technol, Dept Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China; 2.Chinese Acad Sci, CAS Key Lab Receptor Res, Drug Discovery & Design Ctr, Shanghai Inst Mat Med, Shanghai 201203, Peoples R China |
| 推荐引用方式 GB/T 7714 | Ge, Yang,Lu, Yunxiang,Xu, Zhijian,et al. Controlling the spin state of diphenylcarbene via halogen bonding: A theoretical study[J]. INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,2018,118(15). |
| APA | Ge, Yang,Lu, Yunxiang,Xu, Zhijian,&Liu, Honglai.(2018).Controlling the spin state of diphenylcarbene via halogen bonding: A theoretical study.INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY,118(15). |
| MLA | Ge, Yang,et al."Controlling the spin state of diphenylcarbene via halogen bonding: A theoretical study".INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 118.15(2018). |
入库方式： OAI收割
来源：上海药物研究所
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