Supramolecular Fullerene Polymers and Networks Directed by Molecular Recognition between Calix[5]arene and C₆₀

Abstract

A biscalix[5]arene-C60 supramolecular structure was utilized for the development of supramolecular fullerene polymers. Di- and tritopic hosts were developed to generate the linear and network supramolecular polymers through the complexation of a dumbbell-shaped fullerene. The molecular association between the hosts and the fullerene were carefully studied by using (1) H NMR, UV/Vis absorption, and fluorescence spectroscopy. The formation of the supramolecular fullerene polymers and networks was confirmed by diffusion-ordered (1) H NMR spectroscopy (DOSY) and solution viscometry. Upon concentrating the mixtures of di- or tritopic hosts and dumbbell-shaped fullerene in the range of 1.0-10 mmol L(-1) , the diffusion coefficients of the complexes decreased, and the solution viscosities increased, suggesting that large polymeric assemblies were formed in solution. Scanning electron microscopy (SEM) was used to image the supramolecular fullerene polymers and networks. Atomic force microscopy (AFM) provided insight into the morphology of the supramolecular polymers. A mixture of the homoditopic host and the fullerene resulted in fibers with a height of (1.4±0.1) nm and a width of (5.0±0.8) nm. Interdigitation of the alkyl side chains provided secondary interchain interactions that facilitated supramolecular organization. The homotritopic host generated the supramolecular networks with the dumbbell-shaped fullerene. Honeycomb sheet-like structures with many voids were found. The growth of the supramolecular polymers is evidently governed by the shape, dimension, and directionality of the monomers.

π–π interactions in carbon nanostructures

“…6). 26 To that end, the Japanese team synthesized di-and tritopic calixarene hosts, and studied their association to form polymers through a variety of techniques, including NMR, absorption and fluorescence spectroscopy, SEM and AFM. The relevance of a correct shape match between the host and the guest is once more highlighted in the synthesis of a supramolecular polymer with outstanding degree of polymerization based on the interaction between a C 60 fragment and an exTTF-based macrocycle (Fig.…”

Self‐Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand‐Based Coordination Capsules

“…Self-assembled capsules are well-known molecular containers that encapsulate unstable species as well as molecular guests. [13] During the course of our study on the molecular recognition of self-assembled capsules [14] and supramolecular polymers, [15] acavitand-based coordination capsule was found to encapsulate multiple guest binding units on apolymer main chain to modulate the conformation of ap olymer main chain. [16] We envisioned that apolymer-attached coordination capsule poly-1 can bind to the multiple guest sites of polyester poly-(R)-2 to form as upramolecular graft polymer (poly-1) n •poly-(R)-2 possessing eight graft chains at each branching point ( Figure 1a,Scheme 1).…”

Fullerene‐Based Conducting Polymers:n‐Dopable Materials for Charge Storage Application

“…A polymeric network has been covalently modified with host moieties to effectively bond fullerenes and control the organization of fullerene arrays at the molecular level. Corranulene, [31] calix[n]arenes, [91,92] 9,10-di(1,3-dithiol-2ylidene)-9,10-dihydroantacene, [84,[93][94][95][96] methylo-porphirines, [97][98][99] and cyclodextrins [100][101][102][103] moieties exhibit fullerene-encapsulation properties. There are two approaches to form polymeric networks with fullerene encapsulated by host moieties: i) formation of polymeric structures from monomers containing covalently bonded host moiety, and next fullerene incorporation into polymeric structure by "ball-and-socket" type π-π stacking interaction, [31] ii) supramolecular complexation between the host moiety and the guest fullerenes, which results in the formation of an extended polymeric network.…”

“…There are two approaches to form polymeric networks with fullerene encapsulated by host moieties: i) formation of polymeric structures from monomers containing covalently bonded host moiety, and next fullerene incorporation into polymeric structure by "ball-and-socket" type π-π stacking interaction, [31] ii) supramolecular complexation between the host moiety and the guest fullerenes, which results in the formation of an extended polymeric network. [91][92][93][94][95]102] The first procedure was used to form a diblock copolymer co-poly-1 with covalently attached corannulene moiety which is able to effectively hosts fullerene molecules (Scheme 1). This method enables to control desired polymer architectures and composition appropriate for use in a specific applications.…”