Theoretical prediction of the host–guest interactions between novel photoresponsive nanorings and C₆₀: A strategy for facile encapsulation and release of fullerene

Abstract

A series of photoresponsive-group-containing nanorings hosts with 12∼14 Å in diameter is designed by introducing different number of azo groups as the structural composition units. And the host-guest interactions between fullerene C60 and those nanoring hosts were investigated theoretically at M06-2X/6-31G(d)//M06-L/MIDI! and wB97X-D/6-31G(d) levels. Analysis on geometrical characteristics and host-guest binding energies revealed that the designed nanoring molecule (labeled as 7) which is composed by seven azo groups and seven phenyls is the most feasible host for encapsulation of C60 guest among all candidates. Moreover, inferring from the simulated UV-vis-NIR spectroscopy, the C60 guest could be facilely released from the cavity of the host 7 via configuration transformation between trans-form and cis-form of the host under the 563 nm photoirradiation. Additionally, the frontier orbital features, weak interaction regions, infrared, and NMR spectra of the C60@7 host-guest complex have also been investigated theoretically.

Noncovalent interactions between O6‐corona[6]arene nanorings and fullerenes C60 and C70: atypical ring ball‐shaped host‐guest systems

“…The ability of this density functional to predict and explain the supramolecular chemistry of carbon nanohoops and fullerenes at van der Waals distances is very encouraging . All the geometric configurations were fully optimized at the M06‐2X/6‐31G(d) level in vacuum and solvent (toluene), respectively. To ensure the most stable structure being obtained for each of the complexes, the fullerene is placed inside O 6 ‐corona[6]arene ring and rotated stepwisely along the long axis of C 70 , and then, the most stable structure obtained is selected for further analysis.…”

“…Especially, for a nanoscale system, host‐guest interaction may result in novel nanohybrid with new properties and unique functions, which is maybe very different from the individual host or guest molecule . The well‐designed host‐guest complexes have been used to construct various supramolecular function systems, such as novel host systems that can reversibly capture and release guest molecules in a controllable manner …”

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

“…As Hobza pointed, although covalent interactions determine the primary structure of a molecule, the noncovalent interactions are responsible for the tertiary and quaternary structure of a molecule and create the fascinating world of the 3D architectures of supramolecular systems, so dose for those of carbon‐nanostructures. For an instance, driven by convex‐concave π–π noncovalent interactions, quite stable host–guest carbon‐base “peapod” structures can be formed with CNRs or CNTs and fullerenes or endohedral metallofullerenes, and those nanoscale systems possess novel nano‐hybrid with interesting properties and unique functions, which may be very different from the individual components. Using first principle and molecular mechanics methods, our group investigated the noncovalent interaction between nanodiamonds, and found that the binding model is face(111)‐face(111) van der Waals force .…”

Theoretical studies on the structure and thermochemistry of cyclicparaphenylenediazenes

“…Very few theoretical studies have been carried out on CPPDs. 19,26 As far as we know Durgun and Grossman reported the structure and enthalpies of all cis and all trans isomer of cyclic [6]paraphenylenediazenes ([6] CPPD). 19 Recently, Van Raden et al 27 have synthesized highly strained nitrogen-doped cyclicparaphenylenes i.e., aza [6]CPP.…”

“…They calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap level using hybrid DFT at B3LYP/6-31G(d) level. In another study, Yuan et al 26 have predicted the host-guest interaction between [6]CPPD and [7]CPPD with fullerene (C 60 ) using hybrid DFT at M06-L and M06-2X levels. They reported the relative stabilities of host-guest interactions between fullerene C 60 and [6]CPPD and [7]CPPD by varying nitrogen atoms in the ring.…”