New Isolated-Pentagon-Rule Isomer of C₉₂ Isolated as Trifluoromethyl and Chlorido Derivatives: C₉₂(38)(CF₃)_14/16 and C₉₂(38)Cl_20/22

High-temperature trifluoromethylation and chlorination of the C₉₂ fraction followed by single-crystal X-ray diffraction with the use of synchrotron radiation resulted in the structure determination of C₉₂(38)­(CF₃)₁₄, five isomers of C₉₂(38)­(CF₃)₁₆, and C₉₂(38)­Cl_20/22. Their addition patterns are stabilized by the formation of isolated CC bonds and aromatic substructures. According to quantum-chemical calculations, the newly detected <i>C</i>₁–C₉₂(38) belongs to the most stable isomers of C₉₂

New Giant Fullerenes Identified as Chloro Derivatives: Isolated-Pentagon-Rule C₁₀₈(1771)Cl₁₂ and C₁₀₆(1155)Cl₂₄ as well as Nonclassical C₁₀₄Cl₂₄

High temperature chlorination of HPLC fractions of higher fullerenes followed by single crystal X-ray diffraction with the use of synchrotron radiation resulted in the structure determination of IPR C₁₀₆(1155)­Cl₂₄ and IPR C₁₀₈(1771)­Cl₁₂. C₁₀₆(1155)­Cl₂₄ is cocrystallized with C₁₀₄Cl₂₄, a chloride of the nonclassical isomer of C₁₀₄. The moderately stable isomer C₁₀₆(1155) and the most stable C₁₀₈(1771) represent so far the largest pristine fullerenes with known cages

Five Isolated Pentagon Rule Isomers of Higher Fullerene C₉₄ Captured as Chlorides and CF₃ Derivatives: C₉₄(34)Cl₁₄, C₉₄(61)Cl₂₀, C₉₄(133)Cl₂₂, C₉₄(42)(CF₃)₁₆, and C₉₄(43)(CF₃)₁₈

High-temperature chlorination and trifluoromethylation of C₉₄ isomeric mixtures followed by single-crystal X-ray diffraction with the use of synchrotron radiation resulted in the structure determination of C₉₄(34)­Cl₁₄, C₉₄(61)­Cl₂₀, C₉₄(133)­Cl₂₂, C₉₄(42)­(CF₃)₁₆, and C₉₄(43)­(CF₃)₁₈. Their addition patterns are stabilized by the formation of isolated CC bonds and aromatic substructures. Four cage isomers of C₉₄ (nos. 34, 42, 43, and 133) have been experimentally confirmed for the first time

Steering the Geometry of Butterfly-Shaped Dimetal Carbide Cluster within a Carbon Cage via Trifluoromethylation of Y₂C₂@C₈₂(6)

As one of the largest sub-branches of endohedral clusterfullerenes, dimetal carbide clusterfullerene (CCF) in the form of M₂C₂@C_2<i>n</i> is quite intriguing since an alternative structure of M₂@C_2<i>n</i>+2 as conventional dimetallofullerene may exist as well. Herein, by using high-temperature trifluoromethylation followed by HPLC separation and single-crystal X-ray diffraction study, we report for the first time the unambiguous structural determination of yttrium (Y)-based CCF as its trifluoromethyl derivatives, Y₂C₂@C₈₂(6)­(CF₃)₁₆. Four isomers of Y₂C₂@C₈₂(6)­(CF₃)₁₆ with different addition patterns of 16 CF₃ groups are successfully isolated, and two Y atoms of the butterfly-shaped Y₂C₂ cluster are coordinated by two cage pentagons in each isomer. The butterfly geometry of Y₂C₂ cluster varies significantly in the four Y₂C₂@C₈₂(6)(CF₃)₁₆ isomers, with Y···Y distances ranging from 3.544 to 4.051 Å dependent on the relative positions of the two yttrium-coordinated pentagons on the carbon cage

Five Isolated Pentagon Rule Isomers of Higher Fullerene C₉₄ Captured as Chlorides and CF₃ Derivatives: C₉₄(34)Cl₁₄, C₉₄(61)Cl₂₀, C₉₄(133)Cl₂₂, C₉₄(42)(CF₃)₁₆, and C₉₄(43)(CF₃)₁₈

High-temperature chlorination and trifluoromethylation of C₉₄ isomeric mixtures followed by single-crystal X-ray diffraction with the use of synchrotron radiation resulted in the structure determination of C₉₄(34)­Cl₁₄, C₉₄(61)­Cl₂₀, C₉₄(133)­Cl₂₂, C₉₄(42)­(CF₃)₁₆, and C₉₄(43)­(CF₃)₁₈. Their addition patterns are stabilized by the formation of isolated CC bonds and aromatic substructures. Four cage isomers of C₉₄ (nos. 34, 42, 43, and 133) have been experimentally confirmed for the first time

Five Isolated Pentagon Rule Isomers of Higher Fullerene C₉₄ Captured as Chlorides and CF₃ Derivatives: C₉₄(34)Cl₁₄, C₉₄(61)Cl₂₀, C₉₄(133)Cl₂₂, C₉₄(42)(CF₃)₁₆, and C₉₄(43)(CF₃)₁₈

High-temperature chlorination and trifluoromethylation of C₉₄ isomeric mixtures followed by single-crystal X-ray diffraction with the use of synchrotron radiation resulted in the structure determination of C₉₄(34)­Cl₁₄, C₉₄(61)­Cl₂₀, C₉₄(133)­Cl₂₂, C₉₄(42)­(CF₃)₁₆, and C₉₄(43)­(CF₃)₁₈. Their addition patterns are stabilized by the formation of isolated CC bonds and aromatic substructures. Four cage isomers of C₉₄ (nos. 34, 42, 43, and 133) have been experimentally confirmed for the first time

Capturing C₈₄ Isomers as Chlorides and Pentafluoroethyl Derivatives: C₈₄Cl₂₂ and C₈₄(C₂F₅)₁₂

A mixture of higher fullerenes C₇₆–C₉₆ was pentafluoroethylated with C₂F₅I at 250 °C affording a mixture of C₂F₅ derivatives. After separation with high-performance liquid chromatography, the second C₂F₅ derivative of C₈₄(16), C₈₄(C₂F₅)₁₂, was investigated by X-ray crystallography and compared with the known isomer in terms of addition patterns and formation energies. Chlorination of a C₈₄ isomeric mixture with VCl₄ at 350–400 °C resulted in the formation of C₈₄Cl₂₂. X-ray diffraction study revealed the superposition of several C₈₄Cl₂₂ molecules with different isomeric C₈₄ cages but the same chlorination pattern

Capturing C₈₄ Isomers as Chlorides and Pentafluoroethyl Derivatives: C₈₄Cl₂₂ and C₈₄(C₂F₅)₁₂

A mixture of higher fullerenes C₇₆–C₉₆ was pentafluoroethylated with C₂F₅I at 250 °C affording a mixture of C₂F₅ derivatives. After separation with high-performance liquid chromatography, the second C₂F₅ derivative of C₈₄(16), C₈₄(C₂F₅)₁₂, was investigated by X-ray crystallography and compared with the known isomer in terms of addition patterns and formation energies. Chlorination of a C₈₄ isomeric mixture with VCl₄ at 350–400 °C resulted in the formation of C₈₄Cl₂₂. X-ray diffraction study revealed the superposition of several C₈₄Cl₂₂ molecules with different isomeric C₈₄ cages but the same chlorination pattern