Supramolecular hybrids of [60]fullerene and single-wall carbon nanotubes

Noncovalent interactions between purified HiPCO single-wall carbon nanotubes (SWNT) and a [60]fullerene-pyrene dyad, synthesized through a regioselective double-cyclopropanation process, produce stable suspensions in which the tubes are very well dispersed, as evidenced by microscopy characterization. Cyclic voltammetry experiments and photophysical characterization of the suspensions in organic solvents are all indicative of sizeable interactions of the pyrene moiety with the SWNT and, therefore, of the prevalence in solution of [60]fullerene-pyreneSWNT hybrids.     

Dimeric capsules with a nanoscale cavity for [60]fullerene encapsulation

The acid-assisted and guest-induced formation of superstructures was achieved by the addition of haloacetic acids to a toluene solution of the resorcin[4]arene derivatives 1 and [60]fullerenes. The formation of dimeric superstructures that encapsulated a nanosized guest molecule was observed when appropriate acids, such as haloacetic acids, and suitable guest molecules, such as [60]fullerenes, were co-added to a toluene solution of cavitand 1 that has four pyridine units, whereas a complicated equilibrium between several species was detected without [60]fullerenes, and the formation of discrete superstructures was not monitored in the absence of haloacetic acids. The spectroscopic data indicate that the formed [60]fullerene-encapsulated complexes have the structure of 2. These complexes are self-assembled through pyridinium-anion-pyridinium interactions and by pi-pi and van der Waals interactions. The rate of decomplexation of 2 is estimated to be 3.1 s(-1) from a 2D exchange NMR spectrum. The [60]fullerene encapsulation process can be controlled by modifying the amounts of acids used, changing the temperature of the system, altering the ratio of acid/base, and even through varying the solvent polarity. Moreover, the fluorescence spectra show band-narrowing spectral changes and a retardation of the relaxation characteristics of isolated and isotropic [60]fullerenes, which indicates that the environmental change around [60]fullerene is induced upon its encapsulation.     

A Supramolecular Complex in Small-Molecule Solar Cells based on Contorted Aromatic Molecules

"Ball and socket" motif: The contorted dibenzotetrathienocoronene (6-DBTTC) forms a complex with the C(70) fullerene PC(70) BM embedded in an amorphous phase of PC(70) BM. The materials are processable into organic solar cells in solution. The power conversion efficiency is maximal when there is a 1:2 molar ratio of 6-DBTTC to PC(70) BM. Formation of the supramolecular complex directly affects charge separation in the active layer.     

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

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 ¹H NMR, UV/Vis absorption, and fluorescence spectroscopy. The formation of the supramolecular fullerene polymers and networks was confirmed by diffusion‐ordered ¹H 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.     

Supramolecular Assemblies for Electronic Materials

This work presents a synergy between organic electronics and supramolecular chemistry, in which a host–guest complex is designed to function as an efficacious electronic material. Specifically, the noncovalent recognition of a fullerene, phenyl-C₆₁-butyric acid methyl ester ( PC₆₁BM ), by an alternating perylene diimide ( P )-bithiophene ( B ) conjugated macrocycle ( PBPB ) results in a greater than five-fold enhancement in electron mobility, relative to the macrocycle alone. Characterization and quantification of the binding of fullerenes by host PBPB is provided alongside evidence for intermolecular electronic communication within the host–guest complexes.     

Synthesis and photoinduced electron-transfer properties of phthalocyanine-[60]fullerene conjugates

A series of three novel ZnPc-C60 conjugates (Pc=phthalocyanine) 1 a-c bearing different spacers (single, double, and triple bond) between the two electroactive moieties was synthesized and compared to that of ZnPc-C60 conjugate 2, in which the two electroactive moieties are linked directly. The synthetic strategy- towards the preparation of 1 a-c- involved palladium-catalyzed cross-coupling reactions over a monoiodophthalocyanine precursor 4 to introduce the corresponding spacer, and subsequent dipolar cycloaddition reaction to C60. Detailed photophysical investigations of 1 a-c and 2 prompted an intramolecular electron transfer that evolves from the photoexcited ZnPc to the electron-accepting C60. In particular, with the help of femtosecond laser photolysis charge separation was indeed confirmed as the major deactivation channel. Complementary time-dependent density functional calculations supported the spectral assignment, namely, the spectral identity of the ZnPc(*+) radical cation and the C60 (*-) radical anion as seen in the differential absorption spectra. The lifetimes of the correspondingly formed radical ion-pair states depend markedly on the solvent polarity: they increase as polarity decreases. Similarly, although to a lesser extent, the nature of the linker impacts the lifetime of the radical ion-pair states. In general, the lifetimes of these states tend to be shortest in the system that lacks any spacer at all (2), whereas the longest lifetimes were found in the system that carries the triple-bond spacer (1 a).     

Designing liquid-crystalline dendronised hexa-adducts of [60]fullerene via click chemistry

ABSTRACT

Liquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C₆₀) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, ¹H and ¹³C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C₆₀ functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C₆₀ decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C₆₀ is a unique synthetic platform for the design of fullerodendrimers and dendronised materials.     

[60]富勒烯[2＋3]环加成反应的研究进展

对[60]富勒烯[2＋3]环加成反应的研究进展进行了综述，并介绍了在环加成反应中使用的主要试剂及反应机理.     

Controlling the confinement and alignment of fullerene C(70) in para-substituted calix[5]arenes

In toluene fullerene C(70) forms 2:1 complexes with p-benzylcalix[5]arene (1) and p-phenylcalix[5]arene (2), [C(70) subset1(2)].6(C(7)H(8)) and [C(70) subset2(2)].7(C(7)H(8)). The fullerene molecules are completely shrouded by two calix[5]arenes in addition to terminal benzyl groups from other supermolecules, [C(70) subset1(2)], and solvent. Within the capsule-like supermolecules the calixarenes have distinctly different arrangements relative to the principal axis of the fullerene; for [C(70) subset1(2)].6(C(7)H(8)) the oxygen planes of the two calixarenes are skewed by 37.0 and 47.5 degrees , whereas in [C(70) subset2(2)].7(C(7)H(8)) the principal axes of the fullerene and the two encapsulating calixarenes are more closely aligned with the corresponding angles at 9.7 and 8.6 degrees , and features a pentaphenyl inter-calixarene embrace. The Hirshfeld surfaces of these two complexes have been investigated for a detailed understanding of the orientation and nature of interactions of C(70) with the cavitand-type molecules and toluene.     

Amination of [60]fullerene by ammonia and by primary and secondary aliphatic amines--preparation of amino[60]fullerene peroxides

Ammonia and aliphatic amines react readily in the oxygen-rich regions of the Cs symmetric fullerene peroxides C60(O)(OOtBu)4 (1) and C60(OH)(Br)(OOtBu)4 (2 c). Michael addition-type hydroamination of the 1,4-diene moiety on the central skew-pentagon was observed when 1 was treated with ammonia or with nonbulky primary amines, while sterically demanding primary amines opened the epoxy moiety to form vicinal aminohydroxy fullerene compounds with the amino group on the central pentagon. In 2 c the bromo group was replaced under similar conditions by ammonia and primary amines. Cyclic secondary amines showed different reaction patterns, forming hydrogenation products or aminoketal-fullerenes when treated with 1 and 2 c, respectively. Single-electron transfer (SET) is the key step in all the proposed mechanisms. The compounds were characterized by their spectroscopic data, and in addition, three single-crystal X-ray structures were obtained.     

Hydrogen-bonding motifs in fullerene chemistry

The combination of fullerenes and hydrogen-bonding motifs is a new interdisciplinary field in which weak intermolecular forces allow modulation of one-, two-, and three-dimensional fullerene-based architectures and control of their function. This Minireview aims to extend the scope of fullerene chemistry to a truly supramolecular level from which unprecedented architectures may evolve. It is shown that electronic communication in C(60)-based hydrogen-bonded donor-acceptor ensembles is at least as strong as that found in covalently connected systems and that hydrogen-bonding fullerene chemistry is a versatile concept for the construction of functional ensembles.     

Functional organic materials based on polymerized liquid-crystal monomers: supramolecular hydrogen-bonded systems

Functional organic materials are of great interest for a variety of applications. To obtain precise functional properties, well-defined hierarchically ordered supramolecular materials are crucial. The self-assembly of liquid crystals has proven to be an extremely useful tool in the development of well-defined nanostructured materials. We have chosen the illustrative example of photopolymerizable hydrogen-bonding mesogens to show that a wide variety of functional materials can be made from a relatively simple set of building blocks. Upon mixing these compounds with other reactive mesogens, nematic, chiral nematic, and smectic or columnar liquid-crystalline phases can be formed that can be applied as actuators, sensors and responsive reflectors, and nanoporous membranes, respectively.     

Nanofibers of fullerene C60 through interplay of ball-and-socket supermolecules

Mixing solutions of p-tBu-calix[5]arene and C(60) in toluene results in a 1:1 complex (C(60)) intersection(p-tBu-calix[5]arene), which precipitates as nanofibers. The principle structural unit is based on a host-guest ball-and-socket nanostructure of the two components, with an extended structure comprising zigzag/helical arrays of fullerenes (powder X-ray diffraction data coupled with molecular modeling). Under argon at temperatures above 309 degrees C, the fibers undergo selective volatilization of the calixarenes to afford C(60)-core nanostructures encapsulated in a graphitic material sheath, which exhibits a dramatic increase in surface area. Above 650 degrees C the material exhibits an ohmic conductance response, due to the encapsulation process.