Supramolecular nanotubes based on halogen bonding interactions: cooperativity and interaction with small guests

Abstract

In this manuscript we study the formation of a series of self-assembled supramolecular nanotubes (SNTs) governed by noncovalent halogen bonding interactions. We have used eight different belts to construct the nanotubes, which are based on alternating benzene rings with 4-X-pyridine or p-X-benzonitrile rings (X = Br, I). The orientation of the halogen atoms can be parallel (denoted as "all up") or antiparallel (denoted as "up/down"). In addition to the calculation of the formation energies of several binary and ternary assemblies, we have studied the ability of these non-covalently bonded self-organizing nanotubes to incorporate both anions and cations in their interior. We have used the BP86-D3/def2-TZVP level of theory to analyse the large assemblies and the RI-MP2/def2-TZVP level of theory for some model systems. This research emphasizes the role of σ-hole halogen bonds in the design and generation of assembled supramolecular structures and offers an approach for the creation of SNTs.

Tetrel Bonding Interactions in Perchlorinated Cyclopenta- and Cyclohexatetrelanes: A Combined DFT and CSD Study

“…Consequently, the Cambridge Structural Database (CSD) was inspected in a series of studies in order to gain some insights into the impact of this interaction in solid state chemistry [ 9 , 10 ]. The scientific interest regarding this interaction has expanded exponentially due to its recognition as a prominent player in biological media and the design of new materials; leading to a wide amount of theoretical and experimental studies [ 11 , 12 , 13 , 14 ]. In addition, it has been widely recognized that σ-holes (and more recently π-holes [ 15 ]) can also appear in positive electrostatic potential regions involving covalently bond atoms of groups III to VIII [ 16 , 17 , 18 , 19 , 20 , 21 , 22 ].…”

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

“…As a result, the directed assembly of compositionally and structurally complex architectures requires a thorough understanding of the way in which complementary and competing forces eventually lead to a stable solid-state architecture [6,7]. Against this background, our goal was to establish reliable and robust avenues for the design and synthesis of crystalline metal-containing materials by encoding each building-block with structural-preferences that lead to "programmable" and predictable assembly [8][9][10].…”

On the Importance of Halogen–Halogen Interactions in the Solid State of Fullerene Halides: A Combined Theoretical and Crystallographic Study

“…In addition, we have performed AIM (Atoms in Molecules) and NBO (Natural Bonding Orbital) analyses to further characterize the interactions described herein. Finally, we have performed a search in the CSD (Cambridge Structural Database) in order to find experimental evidence of the impact of halogen-halogen interactions on the solid state architectures of halogenated C 60 s. exponentially, due to the recognition of its importance in biological systems and the design of new materials, leading to a plethora of theoretical and experimental studies devoted to this fruitful line of research [22][23][24][25]. Apart from the classical halogen bond, there is growing interest amongst the scientific community to properly understand weaker halogen-halogen interactions [26], which have shown a promising future as stabilizing agents of metal complexes [27,28], by governing the formation of novel solid state architectures [29][30][31] and even tuning the properties of biological and conjugated materials [32][33][34][35].…”