Theoretical Insights for Materials Properties of Cyclic Organic Nanorings

Abstract

The synthesis of new carbon nanoforms with remarkable and fine-tuned bulk properties still represents a formidable challenge, with cyclic organic nanorings emerging in recent years for the template-driven design of this kind of systems. The design and engineering of these materials can be first controlled at the molecular scale, to further induce their specific self-assembly toward tailored properties at the nanoscale. Theoretical studies have lately contributed to the understanding of the underlying physical effects, the development of synthetic strategies, and the rationalization of novel materials properties, employing a variety of methods ranging from accurate calculations of isolated molecules to atomistic molecular dynamics simulations of a large sample of molecules in realistic conditions, which will be reviewed here with a focus on the transition from single-molecule to supramolecular properties.

Highly efficient charge transport across carbon nanobelts

“…Recently, the family of CNBs is further expanded by the synthesis of new forms of CNBs containing nonhexagonal rings (14)(15)(16)(17)(18), heteroatom dopants (15,17,(19)(20)(21)(22), and complex topologies (23,24). These breakthroughs inspire intensive experimental and theoretical explorations of fundamental physical properties associated with the unique belt-shaped structures of CNBs (25)(26)(27)(28). Notably, the radial π-electron delocalization along the highly distorted carbon backbone of CNBs enhances their πconjugation and leads to a small energy gap between their highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) , which demonstrates their potential applications in optoelectronics (1).…”

Charge delocalization and aromaticity of doubly reduced double-walled carbon nanohoops

“…Macrocyclic aromatic carbon structures with curved π-surfaces exhibit exceptional structural and electronic properties with flourishing applications in nanomaterials, organic–electronic devices and supramolecular chemistry. 1–9 Among such structures, cycloparaphenylenes (CPPs), also called nanohoops, are a unique class of polycyclic aromatic hydrocarbons (PAHs) consisting of para-connected benzene rings forming an in-plane macrocyclic π system. They can be conceived as the smallest unit of armchair carbon nanotubes (CNTs), embodying the prospect for “bottom-up” organic synthesis of such single-walled nanomaterials.…”

Chiral Cylindrical Molecule with Absorption Dissymmetry Factor towards Theoretical Limit of 2

“…[ 13 ] Together with the synthetic challenge of these materials, therefore, it is highly important to employ theoretical calculations to establish the structure–property relationship of chiral molecules, and in advance screen the best possible chiral molecules with intrinsically strong chiroptical property prior to synthesis, which could significantly accelerate the discovery of chiral molecules with strong optical chirality and also save the power and time‐cost during material synthesis. [ 14 ] Time‐dependent density functional theory (TDDFT) calculations provide a reliable description and prediction of circular dichroism in many realistic chemical systems, which could satisfy both moderate accuracy and computational efficiency. [ 15 ] In this work, we are aiming to screen the best chiral molecules with intrinsically strong chiroptical properties and establish the structure–performance relationship between the molecular structure and chiroptical property of these molecules based on TDDFT calculations, and hopefully provide some intrinsically strong chiroptical molecules in theory.…”