A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and Inversions

Recently, polycyclic arenes with positive curvature have gained increasing significance in the field of material chemistry. This study specifically explores the inversion barriers of a series of positively curved circulenes by using five-membered heterocycles integrated into the backbone of primitiv...

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Main Authors: Yijian Ma, Tianle Dai, Chengshuo Shen
Format: Article
Language:English
Published: MDPI AG 2024-11-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/29/22/5335
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author Yijian Ma
Tianle Dai
Chengshuo Shen
author_facet Yijian Ma
Tianle Dai
Chengshuo Shen
author_sort Yijian Ma
collection DOAJ
description Recently, polycyclic arenes with positive curvature have gained increasing significance in the field of material chemistry. This study specifically explores the inversion barriers of a series of positively curved circulenes by using five-membered heterocycles integrated into the backbone of primitive [5]circulenes and [6]circulenes. For hetero[5]circulenes, where one benzenoid ring is replaced by a heterocycle, the inversion barriers exhibit a strong correlation with the rotary angles of the heterocycles, and larger rotary angles result in lower inversion barriers. Additionally, the aromaticity of the circulene undergoes a significant reduction during the inversion process. As the number n of replaced rings increases, the inversion barriers can be adjusted, demonstrating an almost linear relationship with n. In the case of hetero[6]circulenes, molecules bearing heterocycles with small rotary angles also show positive curvatures. Furthermore, we examine the relationship between the radii of the fitted sphere for the circulenes and the inversion barriers, revealing an intriguing inverse proportionality between the fourth power of the radius and the inversion barrier. We anticipate that this research will offer a fresh perspective on studies related to positively curved polycyclic arenes.
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spelling doaj-art-e525403436da44eebbff2f78bd3c201b2025-08-20T01:53:57ZengMDPI AGMolecules1420-30492024-11-012922533510.3390/molecules29225335A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and InversionsYijian Ma0Tianle Dai1Chengshuo Shen2School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310000, ChinaSchool of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310000, ChinaSchool of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310000, ChinaRecently, polycyclic arenes with positive curvature have gained increasing significance in the field of material chemistry. This study specifically explores the inversion barriers of a series of positively curved circulenes by using five-membered heterocycles integrated into the backbone of primitive [5]circulenes and [6]circulenes. For hetero[5]circulenes, where one benzenoid ring is replaced by a heterocycle, the inversion barriers exhibit a strong correlation with the rotary angles of the heterocycles, and larger rotary angles result in lower inversion barriers. Additionally, the aromaticity of the circulene undergoes a significant reduction during the inversion process. As the number n of replaced rings increases, the inversion barriers can be adjusted, demonstrating an almost linear relationship with n. In the case of hetero[6]circulenes, molecules bearing heterocycles with small rotary angles also show positive curvatures. Furthermore, we examine the relationship between the radii of the fitted sphere for the circulenes and the inversion barriers, revealing an intriguing inverse proportionality between the fourth power of the radius and the inversion barrier. We anticipate that this research will offer a fresh perspective on studies related to positively curved polycyclic arenes.https://www.mdpi.com/1420-3049/29/22/5335positive curvaturecirculenepolycyclic areneDFT calculation
spellingShingle Yijian Ma
Tianle Dai
Chengshuo Shen
A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and Inversions
Molecules
positive curvature
circulene
polycyclic arene
DFT calculation
title A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and Inversions
title_full A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and Inversions
title_fullStr A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and Inversions
title_full_unstemmed A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and Inversions
title_short A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and Inversions
title_sort theoretical study of positively curved circulenes embedded with five membered heterocycles structures and inversions
topic positive curvature
circulene
polycyclic arene
DFT calculation
url https://www.mdpi.com/1420-3049/29/22/5335
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AT tianledai atheoreticalstudyofpositivelycurvedcirculenesembeddedwithfivememberedheterocyclesstructuresandinversions
AT chengshuoshen atheoreticalstudyofpositivelycurvedcirculenesembeddedwithfivememberedheterocyclesstructuresandinversions
AT yijianma theoreticalstudyofpositivelycurvedcirculenesembeddedwithfivememberedheterocyclesstructuresandinversions
AT tianledai theoreticalstudyofpositivelycurvedcirculenesembeddedwithfivememberedheterocyclesstructuresandinversions
AT chengshuoshen theoreticalstudyofpositivelycurvedcirculenesembeddedwithfivememberedheterocyclesstructuresandinversions