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.     

Morphology Engineering of Fullerene[C70] Microcrystals: From Perfect Cubes,Defective Hoppers to Novel Cruciform-Pillars

Controlled crystallization of fullerene molecules into ordered molecular assemblies is important for their applications. However, the morphology engineering of fullerene[C₇₀] assemblies is challenging, and complicated architectures have rarely been reported due to the low molecular symmetry of C₇₀ molecules, which makes their crystallization difficult to control and the low production yield as well. Herein, with the assistance of solvent intercalation, a general reprecipitation approach is reported to prepare morphologically controllable C₇₀ microcrystals with mesitylene as a good solvent and n-propanol as a poor solvent in one solvent system without replacing specific solvents. A series of C₇₀ microcrystals with high uniformity from perfect cubes and defective hoppers to novel cruciform-pillars are obtained by intentionally tuning C₇₀ concentration and the volume ratio of mesitylene to n-propanol. Among them, novel cruciform-pillar-shaped microcrystals are obtained for the first time by further decreasing the amount of mesitylene in the solvent-intercalated microcrystals. Notably, the C₇₀ concentration is a key parameter for the selective growth of C₇₀ hopper, rather than the volume ratio of mesitylene to n-propanol. Interestingly, the hopper-shaped microcrystals exhibit excellent photoluminescence properties relative to those of cubes and cruciform-pillars owing to the enhanced light absorption, proving their potential applications in optoelectronic devices. This study offers new insights into the morphology-controlled synthesis of other micro/nanostructured organic microcrystals and the fine tuning of photoluminescence properties of organic crystals.     

Thermochemistry of Solvated Crystals of C60> and C70> with o-Xylene

Differential scanning calorimetry (DSC) was used to study the binary systems of C₆₀-o-xylene and C₇₀-o-xylene and the ternary system C₆₀-C₇₀-o-xylene. Fullerene C₆₀ formed solvated crystals C₆₀·2C₈H₁₀ with incongruent melting point 320 K and with enthalpy of decomposition 31±3 kJ (mol of C₆₀)^-1. Two solvated crystals of C₇₀ with incongruent melting points 283 and 369 K, and with decomposition enthalpies 18.5±2.2 and 23.0±1.5 kJ (mol of C₇₀)^-1, were formed from o-xylene solutions. Three ternary compositions with C₆₀/C₇₀ mole ratios of 3:1, 1:1 and 1:3 were scanned by DSC. This revised version was published online in July 2006 with corrections to the Cover Date.     

Responsive vesicles from the self-assembly of crystalline-coil polyferrocenylsilane-block-poly(ethylene oxide) star-block copolymers

We demonstrate the synthesis and characterization of star‐shaped crystalline‐coil block copolymers with four arms consisting of an inner block of poly(ethylene oxide) and an outer semicrystalline compartment of poly(ferrocenyldimethylsilane), [PEO₅₀‐b‐PFDMS₃₅]₄. The materials were synthesized by transition‐metal‐catalyzed ring‐opening polymerization of dimethylsila[1]ferrocenophane in the presence of silane‐functionalized four‐arm PEO stars as macroinitiators and they exhibited a moderate polydispersity (PDI?1.4). Self‐assembly in mixtures of THF and different alcohols as selective solvents for the PEO block resulted in the formation of semicrystalline vesicles (ethanol, 1‐butanol) or large, rather ill‐defined, spherical structures (methanol). Further, both the rate of addition of the selective co‐solvent and the overall solvent/non‐solvent ratio drastically affected the size and stability of the self‐assembled particles. We could also show that a photoacid generator, as a model for an active substance, can be encapsulated and the UV‐induced generation of HCl resulted in a straightforward degradation of the organometallic vesicles.     

Reductive Hydrogenation of Cs‐C70(CF3)8 and C1‐C70(CF3)10

CF₃‐derivatized fullerenes prove once again to be promising scaffolds for regioselective fullerene functionalization: now with the smallest possible addends—hydrogen atoms. Hydrogenation of C_s‐C₇₀(CF₃)₈ and C₁‐C₇₀(CF₃)₁₀ by means of reduction with Zn/Cu couple in the presence of water proceeds regioselectively, yielding only one major isomer of C₇₀(CF₃)₈H₂ and only two for C₇₀(CF₃)₁₀H₂, whose addition patterns are combined in the only abundant isomer of C₇₀(CF₃)₁₀H₄. The observed selectivity is governed by the electronic structure of trifluoromethylated substrates. Interestingly, we discovered that Clar's theory can be utilized to predict the regiochemistry of functionalization, and we look forward to testing it on forthcoming cases of derivatization of pre‐functionalized fullerene building blocks.     

The Interaction of C60, C70, and C60(CN)2 radical anions with cobalt(II) tetraphenylporphyrin in solid multicomponent complexes

A method for the synthesis of the multicomponent ionic complexes: [Cr(I)(C(6)H(6))(2) (.+)][Co(II)(tpp)(fullerene)(-)].C(6)H(4)Cl(2), comprising bis(benzene)chromium (Cr(C(6)H(6))(2)), cobalt(II) tetraphenylporphyrin (Co(II)(tpp)), fullerenes (C(60), C(60)(CN)(2), and C(70)), and o-dichlorobenzene (C(6)H(4)Cl(2)) has been developed. The monoanionic state of the fullerenes has been proved by optical absorption spectra in the UV/vis/NIR and IR ranges. The crystal structures of the ionic [[Cr(I)(C(6)H(6))(2)](.+)](1.7)[[Co(II)(tpp)(C(60))](2)](1.7-). 3.3 C(6)H(4)Cl(2) and [[Cr(I)(C(6)H(6))(2)] (.+)](2)[Co(II)(tpp)[C(60)(CN)(2)]](-)[C(60)(CN)(2) (.-)]).3 C(6)H(4)Cl(2) are presented. The essentially shortened Co.C(fullerene) bond lengths of 2.28-2.32 A in these complexes indicate the formation of sigma-bonded [Co(II)(tpp)][fullerene](-) anions, which are diamagnetic. All the ionic complexes are semiconductors with room temperature conductivity of 2 x 10(-3)-4 x 10(-6) S cm(-1), and their magnetic susceptibilities show Curie-Weiss behavior. The neutral complexes of Co(II)(tpp) with C(60), C(60)(CN)(2), C(70), and Cr(0)(C(6)H(6))(2), as well as the crystal structures of [Co(II)(tpp)](C(60)).2.5 C(6)H(4)Cl(2), [Co(II)(tpp)](C(70)). 1.3 CHCl(3).0.2 C(6)H(6), and [Cr(0)(C(6)H(6))(2)][Co(II)(tpp)] are discussed. In contrast to the ionic complexes, the neutral ones have essentially longer Co.C(fullerene) bond lengths of 2.69-2.75 A.     

Tether‐Directed Bisfunctionalization Reactions of C60 and C70

Four easily isolable regio‐ and stereoselective bis‐adducts of C₆₀ and C₇₀, as well as a new C₇₀‐dumbbell derivative, have been synthesized by using two different bismalonate tethered moieties. The derivatives that possess relatively long‐tethered moieties show highly symmetric addition patterns, as evidenced by spectroscopic measurements, whereas the derivatives possessing the shorter‐tethered moiety exhibit interesting addition patterns on C₆₀ and C₇₀.     

Heterometallic Complexes with Gold(I) Metalloligands: Self‐Assembly of Helical Dimers Stabilized by Weak Intermolecular Interactions and Solvophobic Effects

New gold(I) alkynyl metalloligands bpylC?CAuL, bpyl′C?CAuPPh₃, and PPN[Au(C?Cbpyl′)₂] (bpyl or bpyl′=2,2′‐bipyridin‐5‐yl or ?4‐yl, respectively; L=PMe_xPh_3?x (x=1–3), P(C₆H₃Me₂‐3,5)₃, PCy₃, XyNC) have been synthesized. Ligands bpylC?CH and metalloligands bpylC?CAuL (L=PPh₃, PMePh₂, PCy₃, CNXy) react with MX₂ (M=Fe, Zn, X=ClO₄; M=Co, X=BF₄) to give complexes [M(bpylC?CZ)₃]X₂ (Z=H or AuL). In most cases, these complexes are mixtures of fac and mer isomers in a statistical distribution, in both CH₂Cl₂ and MeCN. However, for L=PPh₃, the fac isomer is dominant in MeCN. NMR and ESI‐MS studies, together with the crystal structure of [Co(bpylC?CAuPPh₃)₃](BF₄)₂, suggest that this solvent dependence is originated by the formation of helical dimers between two fac complexes in MeCN. These dimers are stabilized by solvophobic effects and multiple intermolecular interactions. Complex [Fe(Ph₃PAuC?CbpdiylC?CAuPPh₃)₃](ClO₄)₂ (bpdiyl=2,2′‐bipyridin‐5,5′‐diyl) was obtained by reaction of three diauro diethynylbipyridines and Fe(ClO₄)₂.     

The Molecularly Controlled Synthesis of Ordered Bi‐dimensional C60 Arrays

Much of the research effort concerning the nanoscopic properties of clays has focused on its mechanical applications, for example, as nanofillers for polymer reinforcement. To broaden the horizon of what is possible by exploiting the richness of clays in nanoscience, herein we report a bottom‐up approach for the production of hybrid materials in which clays act as the structure‐directing interface and reaction media. This new method, which combines self‐assembly with the Langmuir–Schaefer technique, uses the clay nanosheets as a template for the grafting of C₆₀ into a bi‐dimensional array, and allows for perfect layer‐by‐layer growth with control at the molecular level. In contrast to the more‐common growth of C₆₀ arrays through nanopatterning, our approach can be performed under atmospheric conditions, can be upscaled to areas of tenths of cm², and can be applied to almost any hydrophobic substrate. Herein, we report a detailed study of this approach by using temperature‐dependent X‐ray diffraction, spectroscopic measurements, and STM.