Van Der Waals heterogeneous layer‐layer carbon nanostructures involving π···H‐C‐C‐H···π···H‐C‐C‐H stacking based on graphene and graphane sheets. Issue 10 (6th February 2017)

• Record Type: Journal Article
• Authors: Yuan, Kun; Zhao, Rui‐Sheng; Zheng, Jia‐Jia; Zheng, Hong; Nagase, Shigeru; Zhao, Sheng‐Dun; Liu, Yan‐Zhi; Zhao, Xiang
• Is Part Of: Journal of computational chemistry. Volume 38:Issue 10(2017)
• Page Start: 730
• Page End: 739
• Publication Date: 2017-02-06
• Subjects: heterogeneous layer‐layer structure -- C‐H···π stacking interaction -- graphane sheet -- group additivity -- theoretical calculation; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.24743
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : Noncovalent interactions involving aromatic rings, such as π···π stacking, CH···π are very essential for supramolecular carbon nanostructures. Graphite is a typical homogenous carbon matter based on π···π stacking of graphene sheets. Even in systems not involving aromatic groups, the stability of diamondoid dimer and layer‐layer graphane dimer originates from C − H···H − C noncovalent interaction. In this article, the structures and properties of novel heterogeneous layer‐layer carbon‐nanostructures involving π···H‐C‐C‐H···π···H‐C‐C‐H stacking based on [ n ]‐graphane and [ n ]‐graphene and their derivatives are theoretically investigated for n = 16–54 using dispersion corrected density functional theory B3LYP‐D3 method. Energy decomposition analysis shows that dispersion interaction is the most important for the stabilization of both double‐ and multi‐layer‐layer [ n ]‐graphane@graphene. Binding energy between graphane and graphene sheets shows that there is a distinct additive nature of CH···π interaction. For comparison and simplicity, the concept of H‐H bond energy equivalent number of carbon atoms (noted as NHEQ), is used to describe the strength of these noncovalent interactions. The NHEQ of the graphene dimers, graphane dimers, and double‐layered graphane@graphene are 103, 143, and 110, indicating that the strength of C‐H···π interaction is close to that of π···π and much stronger than that of C‐H···H‐C in large size systems. Additionally, frontier molecular orbital, electron density difference and visualized noncovalent interaction regions are discussed for deeply understanding the nature of the C‐H···π stacking interaction in construction of heterogeneous layer‐layer graphane@graphene structures. We hope that the present study would be helpful for creations of new functional supramolecular materials based on graphane and graphene carbon nano‐structures. © 2017 Wiley Periodicals, Inc. Abstract : The structures and properties of novel heterogeneous layer‐layer carbon‐nanostructures involving π···H‐C‐C‐H···π···H‐C‐C‐H stacking based on graphane and graphene sheets and their derivatives are theoretically investigated. Because of relative strong binding between sheets, they should be parallel to the homogenous layer‐layer structure formed by graphene sheets like graphite.