Complexation of Triptycene-Based Macrotricyclic Host toward (9-Anthracylmethyl)benzylammonium Salt: A Ba²⁺ Selective Fluorescence Probe

Abstract

A new triptycene-based macrotricyclic host containing two dibenzo-30 crown-10 moieties (1) has been synthesized. It could form a 1:2 stable complex 1 x 3(2) with (9-anthracylmethyl)benzylammonium salt (3) in both solution and solid state, in which the 9-anthracyl groups were selectively positioned inside the cavity of the host. Moreover, the complexation and disassociation of complex 1 x 3(2) could be chemically controlled by the addition of base and acid. It was also found that Ba(2+) ion could considerably induce the fluorescence enhancement of complex 1 x 3(2), which might thus be utilized as a selective supramolecular fluorescence probe for Ba(2+) ion. Fluorescence and (1)H NMR spectroscopic titrations further showed that the complexation between complex 1 x 3(2) and barium ions underwent a two-step process.

Recent Developments in Synthesis and Applications of Triptycene and Pentiptycene Derivatives

“…Inspired by the fact that crown ethers can not only form complexes with metal ions, but can also show specific complexation capabilities with secondary ammonium ions or paraquats, we designed and synthesized several different kinds of novel triptycene-derived crown ethers -including the triptycene-derived macrotricyclic polyethers 77, [58] 78, [59] and 79, [60] the triptycene-derived tris(crown ether)s 80 [61] and 81, [62] the triptycene-derived molecular tweezers 82, [63] 83, [64] and 84, [65] and the triptycene-derived bismacrotricyclic host 85 [66] (Figure 19) -by treatment of the corresponding polyhydroxytriptycenes with ditosylate com-pounds under high-dilution conditions. Their structures were all confirmed by 1 H NMR and 13 C NMR spectroscopy, mass spectrometry, and elemental analysis.…”

“…1 H NMR experiments and a single-crystal structure showed that in the complex the two 9-anthracyl groups were selectively positioned outside the cavity of the host 77 ( Figure 30). [59] On the basis of the above results, we further tried to synthesize interlocked molecules that might act as molecular machines and intelligent materials. The complexation and disassociation of the complex 78·(115b) 2 could be chemically controlled by addition of base and acid.…”

A Four‐Armed Unsymmetrical Cryptand: From Two Different Host–Guest Interactions to Responsive Supramolecular Polymer

“…The assemblies between cryptand 1 and dibenzylammonium salt 3 were also confirmed by the clear NOE correlation between proton H 1c of host 1 and proton H 3a of guest 3 (Figure S17, Supporting Information). [5a‐d,8a,b]…”

“…For example, Gibson and co‐workers reported the synthesis of the cylindrical four‐armed BMP32C10‐based cryptand, and two of the same paraquat guests could be contained inside the cavity in 2005 . In 2010, Chen and co‐workers reported another typical symmetric four‐armed DB24C8‐based cryptand, and two dibenzylammonium salt guests could thread into the DB24C8 cavity of cryptand …”

Complexation of Triptycene-Derived Macrotricyclic Host with π-Extended Viologens

“…我们还发现带有羟基的客体 5 也可以与大三环主体 1 形成超分子聚准[3]轮烷(1•5) n (图 S44) [13] , 络合模式与 向大环的冠醚空腔(图 S45) [13] , 这种络合模式与大三环 [13] , 这与溶液中 结果是一致的. 4 实验部分 主体 1 [14] 与客体 3 [15] 、4 [16] 、6 [11] 以及(E)-1,2-二(4-吡啶基)乙烯 [17] , 1,4-二(吡啶-4-基)苯 [18] 按照文献方法合 成. H 4.47, N 4.14; found C 39.15, H 4.11, N 4.15. …”