▎ 摘　　要

Noncovalent interactions involving aromatic rings, such as pi center dot center dot center dot pi stacking, CH center dot center dot center dot pi are very essential for supramolecular carbon nanostructures. Graphite is a typical homogenous carbon matter based on pi center dot center dot center dot pi stacking of graphene sheets. Even in systems not involving aromatic groups, the stability of diamondoid dimer and layer-layer graphane dimer originates from C2H center dot center dot center dot H2C noncovalent interaction. In this article, the structures and properties of novel heterogeneous layer-layer carbon-nanostructures involving pi center dot center dot center dot H-C-C-H center dot center dot center dot pi center dot center dot center dot 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 center dot center dot center dot pi 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 center dot center dot center dot pi interaction is close to that of pi center dot center dot center dot pi and much stronger than that of C-H center dot center dot center dot 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 center dot center dot center dot pi 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. (C) 2017 Wiley Periodicals, Inc.