Quantum-Chemical Insights into the Self-Assembly of Carbon-Based Supramolecular Complexes

Abstract

Understanding how molecular systems self-assemble to form well-organized superstructures governed by noncovalent interactions is essential in the field of supramolecular chemistry. In the nanoscience context, the self-assembly of different carbon-based nanoforms (fullerenes, carbon nanotubes and graphene) with, in general, electron-donor molecular systems, has received increasing attention as a means of generating potential candidates for technological applications. In these carbon-based systems, a deep characterization of the supramolecular organization is crucial to establish an intimate relation between supramolecular structure and functionality. Detailed structural information on the self-assembly of these carbon-based nanoforms is however not always accessible from experimental techniques. In this regard, quantum chemistry has demonstrated to be key to gain a deep insight into the supramolecular organization of molecular systems of high interest. In this review, we intend to highlight the fundamental role that quantum-chemical calculations can play to understand the supramolecular self-assembly of carbon-based nanoforms through a limited selection of supramolecular assemblies involving fullerene, fullerene fragments, nanotubes and graphene with several electron-rich π-conjugated systems.

Investigation of the Nature of Intermolecular Interactions in Tetra(thiocyanato)corrolato-Ag(III) Complexes: Agostic or Hydrogen Bonded?

“…The C–H···Ag interaction in the crystal lattice of compound 1 has been investigated in detail with quantum chemical calculations. We incepted the process by optimizing the positions of hydrogen atoms in the monomer and the dimer by using the RI-B97-D3 functional with the cc-pVDZ basis set for C, N, H, and O and the def2-TZVP basis set for Ag. − For both cases, the molecular charge was considered zero, and the optimizations were performed in the closed-shell electronic configurations. As all the electrons are paired in the square planar d 8 Ag­(III) complexes, these molecules are singlet in the ground state.…”

Transient and elusive intermediate states in self‐assembly processes: An overview

“…In this section, we introduce a spectrum of theoretical methods, including Molecular dynamics (MD) simulation, [17] Brownian dynamics (BD) simulation, [18] Monte Carlo (MC) simulation, [19] density functional theory (DFT) calculation, [20] stochastic model, [21] electronic Hamiltonian model, [22] and quantum chemical calculation (QCC). [23] These approaches provide comprehensive insights of how intermediates impact the final structures and properties in self-assembly. These theoretical methods complement experimental studies, giving us a deeper understanding of the selfassembly process.…”

Computational Tools to Rationalize and Predict the Self-Assembly Behavior of Supramolecular Gels

“…Additionally, solvent effects (if any) are included by implicit continuum models or explicitly by molecular mechanics methods (QM/MM). Among the many quantum mechanical theories available, density functional theory (DFT) has established itself as the primary quantum mechanical workhorse to investigate supramolecular systems [ 17 , 18 , 19 ]. The popularity of DFT can be attributed to its favorable balance between accuracy and computational cost, its flexibility (i.e., a myriad of exchange correlation functionals are developed to address different problems) and its ease of use (i.e., several user-friendly software packages exist, to set up a DFT calculations in a matter of seconds).…”