Trapping an unprecedented Ti₃C₃ unit inside the icosahedral C₈₀ fullerene: a crystallographic survey

Abstract

An unexpected cyclopropanated C3-ring coordinating with a Ti3-unit is successfully entrapped inside the icosahedral-C80 cage.

Endohedral Metallofullerenes: New Structures and Unseen Phenomena

“…Moreover, a very recent report demonstrated that an unprecedented Ti 3 C 3 unit can also be entrapped into a I h (7)‐C 80 cage to form a stable compound, Ti 3 C 3 @ I h (7)‐C 80 (Figure d), which is produced by the most efficient arc discharge method . Unexpectedly, X‐ray results unambiguously revealed that the C 3 unit adopts a cyclopropane‐like structure, and its plane is nearly perpendicular to that of the three titanium atoms, indicative of a unique coordination fashion between carbon and titanium.…”

“… X‐ray structures of (a) U 2 C@ I h (7)‐C 80 , (b) Lu 2 TiC@ I h (7)‐C 80 , (c) Sc 2 TiC@ I h (7)‐C 80 , and (d) Ti 3 C 3 @ I h (7)‐C 80 . U, Lu, Ti, Sc, and the internal C atoms are highlighted in azure, purple, gray, luminous yellow, and pale green, respectively.…”

Stabilizing a three-center single-electron metal–metal bond in a fullerene cage

“…Endohedral clusterfullerenes featuring encapsulation of an unstable metallic cluster within a fullerene cage have been attracting considerable interest over the past two decades due to the versatility of the types of encapsulated cluster and its charge transfer to the outer fullerene cage. [1][2][3][4][5][6][7][8] Soon aer the discovery of Sc 3 N@C 80 as the rst endohedral clusterfullerene encapsulating a trimetallic nitride cluster in 1999, 9 the rst metal carbide clusterfullerene (CCF), Sc 2 C 2 @C 84 , was identied by Shinohara and coworkers in 2001. 10 The identication that a C 2 moiety can be encapsulated in the form of metal carbide revealed a competition between CCFs M 2 C 2 @C 2nÀ2 and genuine dimetallofullerenes (di-EMFs) M 2 @C 2n in the hot carbon vapor during the fullerene formation.…”

Combinatorics of Supergiant Fullerenes: Enumeration of Polysubstituted Isomers, Chirality, Nuclear Magnetic Resonance, Electron Spin Resonance Patterns, and Vibrational Modes from C70to C150000

“…Pioneered by the Nobel-winning discovery of Buckminsterfullerene, C 60, several studies have focused on the formation and synthesis, − chirality, ,− spherical aromaticity, ,− electronic and spectroscopic properties of both large fullerenes and their derivatives, − orbitals, aromaticity, and related properties of larger fullerenes, nanomaterials, and related benzenoids, − culminating into a recent combinatorial design of molecular seeds for chirality-controlled synthesis of nanotubes . Owing to the aesthetic beauty of the spherical dome and icosahedral symmetry of many of the fullerene molecular structures, several studies have been carried out on symmetry, combinatorics, chirality, enumeration of conjugated circuits and ring currents, aromaticity, spherical aromaticity, and superaromaticity, and polysubstituted isomers along with graph and group theoretical studies of fullerenes over the years. − <...…”

“…The current study on combinatorics of giant fullerenes up to C 150000 have been stimulated by numerous experimental and theoretical studies on giant fullerenes and onions of giant fullerenes, ,,,,,, where onions are structures with smaller fullerenes such as C 60 encapsulated into giant fullerenes. These onions and giant fullerene cages are also interesting as they exhibit ideal pore sizes to encapsulate metallic oxides as well as small clusters inside fullerenes such as C 180 and C 240 , − ,, and they also find applications in environmental remediation of high-level nuclear wastes. − We note that many artificial intelligence and machine-learning techniques rely on combinatorial recursive generation of large data sets for training . The larger members of icosahedral golden giant series of fullerenes with the formula C 60 m 2 generate a series of C 540, C 960 , C 1500 , C 2940 , ···, C 150000 , etc.…”