Rigid Tether Directed Regioselective Synthesis and Crystallographic Characterization of Labile 1,2,3,4‐Bis(triazolino)[60]fullerene and Its Thermolized Derivatives

Publisher: John Wiley & Sons Inc

E-ISSN: 1521-3757|128|39|12066-12070

ISSN: 0044-8249

Source: ANGEWANDTE CHEMIE, Vol.128, Iss.39, 2016-09, pp. : 12066-12070

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Abstract

AbstractLabile bis‐triazoline adducts of C60 are supposed to be the precursors of bis‐azafulleroids, but the formation mechanism is still unclear because of the incomplete isolation of the thermolized products and the lack of X‐ray structures. A rigid‐tethered reagent 1,2‐bis(azidomethyl)benzene (1) was used to regioselectively synthesize the labile 1,2,3,4‐bis(triazolino)[60]‐fullerene (2), the structure of which was determined by single‐crystal X‐ray crystallography. Further thermolysis of 2 produces four products (3 a–3 d), which were all characterized by X‐ray crystallography. Although 3 a and 3 b have traditional bis‐azafulleroid structures, as proposed previously, 3 c and 3 d show unprecedented structures with either the coexistence of [5,6]‐open and [6,6]‐closed patterns or an oxidized structure with an 11‐membered ring on the cage. A thermolysis mechanism is proposed to clarify long‐term confusion about the transformation process from bis‐triazoline adducts to bis‐azafulleroids of C60.