Irina D. Yushina, Artëm E. Masunov, Ekaterina V. Bartashevich
{"title":"二次谐波发生材料计算设计中的共价有机框架:四元原子及其相互作用的作用","authors":"Irina D. Yushina, Artëm E. Masunov, Ekaterina V. Bartashevich","doi":"10.1021/acs.jpca.4c04633","DOIUrl":null,"url":null,"abstract":"Modern approaches to the design of nonlinear optical materials often rely on computational techniques. Here, we discuss the effects of the variation in the center tetrel atoms, Tt = C, Si, or Ge, in a series of covalent organic frameworks of the COF-102 family. The effects of halogen substitution, Hal = Cl, Br, or I on intramolecular tetrel bonding are also discussed. The characteristics of the calculated electron density have been implemented to describe the features of the electron distribution around the central fragment involving a tetrahedral tetrel atom. The effect of the central Tt atom leads to a dramatic change in the character of electron delocalization on the Tt–C<sub>ar</sub> bond with aromatic rings. The location of the halogen atom at the <i>ortho</i>-position of the aromatic ring leads to the formation of tetrel bonds, halogen bonds, or other noncovalent interactions. The changes in the second-order electric susceptibility χ(2) have been studied in order to describe the strength of nonlinear optical properties within the periodic couple-perturbed Kohn–Sham approach. A counterintuitive trend for the χ(2) decrease is observed upon substitution of H > Cl > Br > I at the <i>ortho</i>-position of the phenyl ring. This is due to the corresponding elongation of the Tt–C<sub>ar</sub> bond.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Covalent Organic Frameworks in Computational Design of Second-Harmonic Generation Materials: Role of Tetrel Atoms and Their Interactions\",\"authors\":\"Irina D. Yushina, Artëm E. Masunov, Ekaterina V. Bartashevich\",\"doi\":\"10.1021/acs.jpca.4c04633\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Modern approaches to the design of nonlinear optical materials often rely on computational techniques. Here, we discuss the effects of the variation in the center tetrel atoms, Tt = C, Si, or Ge, in a series of covalent organic frameworks of the COF-102 family. The effects of halogen substitution, Hal = Cl, Br, or I on intramolecular tetrel bonding are also discussed. The characteristics of the calculated electron density have been implemented to describe the features of the electron distribution around the central fragment involving a tetrahedral tetrel atom. The effect of the central Tt atom leads to a dramatic change in the character of electron delocalization on the Tt–C<sub>ar</sub> bond with aromatic rings. The location of the halogen atom at the <i>ortho</i>-position of the aromatic ring leads to the formation of tetrel bonds, halogen bonds, or other noncovalent interactions. The changes in the second-order electric susceptibility χ(2) have been studied in order to describe the strength of nonlinear optical properties within the periodic couple-perturbed Kohn–Sham approach. A counterintuitive trend for the χ(2) decrease is observed upon substitution of H > Cl > Br > I at the <i>ortho</i>-position of the phenyl ring. This is due to the corresponding elongation of the Tt–C<sub>ar</sub> bond.\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpca.4c04633\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.4c04633","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Covalent Organic Frameworks in Computational Design of Second-Harmonic Generation Materials: Role of Tetrel Atoms and Their Interactions
Modern approaches to the design of nonlinear optical materials often rely on computational techniques. Here, we discuss the effects of the variation in the center tetrel atoms, Tt = C, Si, or Ge, in a series of covalent organic frameworks of the COF-102 family. The effects of halogen substitution, Hal = Cl, Br, or I on intramolecular tetrel bonding are also discussed. The characteristics of the calculated electron density have been implemented to describe the features of the electron distribution around the central fragment involving a tetrahedral tetrel atom. The effect of the central Tt atom leads to a dramatic change in the character of electron delocalization on the Tt–Car bond with aromatic rings. The location of the halogen atom at the ortho-position of the aromatic ring leads to the formation of tetrel bonds, halogen bonds, or other noncovalent interactions. The changes in the second-order electric susceptibility χ(2) have been studied in order to describe the strength of nonlinear optical properties within the periodic couple-perturbed Kohn–Sham approach. A counterintuitive trend for the χ(2) decrease is observed upon substitution of H > Cl > Br > I at the ortho-position of the phenyl ring. This is due to the corresponding elongation of the Tt–Car bond.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.