Molecular tectonics: anion control of dimensionality and connectivity in meta-pyridyl appended tetramercaptotetrathiacalix[4]arene based silver coordination networks

Abstract

The combination of the same organic tecton 1, a meta-pyridyl appended tetramercaptotetrathiacalix[4]arene in 1,3-alternate conformation offering four pyridyl units and eight thioether groups, with three silver salts AgX (X = BF4(-), NO3(-) and SbF6(-)) leads, under identical conditions (concentration, temperature and solvent system), to the formation of different silver coordination networks. Both the connectivity and the dimensionality of the three silver coordination networks depend on the nature of the anion used as a counter ion. Whereas the weakly coordinating BF4(-) anion does not participate in the formation of the non-tubular 1D coordination network, the coordinating NO3(-) anion is bound to the metal cation and this leads to the formation of a tubular 1D silver coordination network. In both cases, the eight S atoms of the tecton 1 do not take part in the binding of the cation. In marked contrast, when the SbF6(-) anion is used as a counter ion, the organic tecton 1 behaves as a tetrakismonodentate through its four meta-pyridyl moieties and as a bischelating unit of the SCCS type leading thus to the formation of a porous 3D diamondoid-type network.

The Role of Calix[n]arenes and Pillar[n]arenes in the Design of Silver Nanoparticles: Self-Assembly and Application

“…The geometry of the final self-assembly was determined by both structural and coordination features of the organic tecton. The authors suggested that the obtained perspective molecular architectures can be used in catalysis, optics, electronics and magnetism [73][74][75][76][77][78][79][80][81][82].…”

Molecular Tectonics: 1D Tubular Type and 3D Diamond Like Mercury(II) Coordination Polymers Based on Pyridyl Appended p-tert-Butyltetrathiacalix[4]arene

“…However, for both TCA and TMTCA, the presence of bridging S atoms not only leads to an enhancement of the size of the macrocycle cavity but also provides additional coordinating sites. Tetrasubstituted thiacalix[4]arene derivatives bearing cyano, [17][18][19] carboxyl, [20][21][22] pyridyl, [23][24][25][26][27][28] coordinating groups were combined with metal cations for the formation of coordination networks displaying a variety of dimensionalities (1D-3D). In contrast to CA, for these sulfur containing tectons, only the 1,3-alternate conformation has been used.…”

“…Furthermore, it has been demonstrated that the dimensionality of the resulting network may be controlled either by the localization of the N atoms or by the nature of the counter ions. [23,27] Here, we report on the preparation of two new coordination networks obtained by combining pyridyl TCA Pyridyl TCA based tectons 3, 4, 5. [23] derivatives in 1,3-alternate conformation 4 (N atom of the pyridyl in meta position) and 5 (N atom of the pyridyl in para position) ( Figure 2) with HgCl 2 , acting as V-shape twoconnecting metallatecton.…”

Depletion forces in single phase and multi-phase complex fluids

“…1. The same weak noncovalent interactions have to be considered together with curvature and packing in molecular tectonics [29,30]. The influence of "weaker" forces triggers the formation of weaker thermodynamically stable structured aggregates, which will be the topic of next special issue of current opinion, to appear in 2016.…”