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. 2019 Oct 14;10(47):10925-10930.
doi: 10.1039/c9sc04315b. eCollection 2019 Dec 21.

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

Pengyuan Yu  1 , Wangqiang Shen  1 , Lipiao Bao  1 , Changwang Pan  1 , Zdenek Slanina  1 , Xing Lu  1
Affiliations

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

Pengyuan Yu et al. Chem Sci. .

Abstract

The sub-nanometer cavity of fullerene cages is an ideal platform to accommodate otherwise unstable species for accurate structural characterization with, for example, rather accurate single crystal X-ray diffraction (XRD) crystallography. Herein, we report the successful entrapment of an isolated Ti3C3 moiety inside the icosahedral-C80 cage to form Ti3C3@Ih-C80 via an arc-evaporation process in the gas phase. The single crystal XRD crystallographic results unambiguously reveal that the C3-unit adopts an unprecedented cyclopropane-like structure which coordinates with the three titanium atoms in an unexpected fashion where the triangular C3-unit is nearly perpendicular to the Ti3-plane. The intercalation of a cyclopropanated C3-unit into the titanium layer is thus unambiguously confirmed. The theoretical results reveal that the Ti3C3 cluster transfers six electrons to the Ih-C80 cage so that each titanium atom has a positive charge slightly above +2 and the C3-unit is negatively charged with about -1. It is noteworthy that this is the first observation of the cyclopropane-coordination fashion in any reported organometallic complex, providing new insights into coordination chemistry.

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Figures

Fig. 1
Fig. 1. (a) MALDI-TOF mass spectrum of purified Ti3C3@Ih-C80. The insets show the experimental and theoretical isotopic distributions of Ti3C83. (b) Vis-NIR absorption spectrum of Ti3C3@Ih-C80 recorded in CS2. A photograph of the corresponding solution is shown in the inset.
Fig. 2
Fig. 2. ORTEP drawing of Ti3C3@Ih-C80·[NiII(OEP)] with 15% thermal ellipsoids. Only the major Ti3C3 site is shown. Solvent molecules and H atoms are omitted for clarity.
Fig. 3
Fig. 3. Orthogonal views showing the relative position of the major Ti3C3 site to the closest cage portions.
Fig. 4
Fig. 4. (a) The optimized Ti3C3 configuration at the B3LYP/3-21G∼SDD level and (b) geometry configuration of the major site of the Ti3C3 cluster from X-ray results.
Fig. 5
Fig. 5. CV curve of Ti3C3@Ih-C80. Conditions: working electrode, glassy carbon electrode; counter electrode, Pt wire; reference electrode, Ag wire; supporting electrolyte, 0.05 M TBAPF6 in o-DCB with ferrocene as the internal standard. Scan rate: 100 mV s–1.
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