Triptycene-Based Expanded Oxacalixarenes:  Synthesis, Structure, and Tubular Assemblies in the Solid State

Abstract

Owing to the unique 3D rigid structure of triptycene, two novel expanded oxacalixarenes 5a and 5b as a pair of diastereomers were efficiently synthesized in a single step by the SNAr reaction of 2,7-dihydroxytriptycene with 2,3,5,6-tetrachloropyridine in the presence of cesium carbonate. Similarly, two pairs of other triptycene-based expanded oxaxalixaenes 7a,7b and 9a,9b could also be obtained by the SNAr reactions of 2,7-dihydroxytriptycene with 1,5-difluoro-2,4-dinitrobenzene and cyanuric chloride, respectively. The structures of the expanded oxacalixarenes were studied by NMR, MS spectra, and X-ray crystal structure analyses. It was found that the expanded oxacalixarene 9b showed a dynamic interconversion between boat and chair conformations. Moreover, we also found that the expanded oxacalixarenes 5a, 5b, and 9a could all assemble into organic tubular structures and further porous architectures in the solid state, in which chlorine bonding, such as C-Cl...Cl, C-Cl...O, and C-Cl...pi interactions, played an important role.

Synthesis, Structure and Conformation of Terphenylene‐Derived Oxacalixaromatics

“…Chen and coworkers introduced triptycene units into the heterocalix[4]-aromatic system, which resulted in several new triptycenecontaining heterocalix [4]aromatics with enlarged cavities and fixed conformations, and found that this class of heterocalix [4]aromatic compounds could encapsulate a number of different guest species. [7] In the second strategy, more aromatic rings are introduced into the heterocalix[4]aromatic scaffolds. In this regard, several larger heterocalix[n]-aromatics [n Ͼ 4] have been constructed [4m,8] and the guest complexation behaviour of some larger heterocalix[n]aromatics [n Ͼ 4] have been evaluated.…”

Synthesis of Substituted Iptycenes

“…When the amounts of dichloro(methoxy)methane and aluminum chloride were increased further, a pair of triformyltriptycene isomers was obtained. Treatment of triptycene (1) with 15 equivalents of dichloro(methoxy)methane in the presence of 15 equivalents of aluminum chloride gave 2,6,14-triformyltriptycene (26) and 2,7,14-triformyltriptycene (27) in 65% and 20% yield, respectively (Scheme 11c).…”

Synthesis of and ion recognition by the novel Schiff base macrocyclic compounds containing triazine

“…Triazine macrocyclic compounds demonstrated high potential application in molecular recognition [14][15][16][17][18][19]. However, this did not refer to Schiff base containing macrocycles [20,21].…”