Heat-Set Gel-like Networks of Lipophilic Co(II) Triazole Complexes in Organic Media and Their Thermochromic Structural Transitions

摘要

A novel class of thermally responsive supramolecular assemblies is formed from the lipophilic cobalt(II) complexes of 4-alkylated 1,2,4-triazoles. When an ether linkage is introduced in the alkylchain moiety, a blue gel-like phase is formed in chloroform, even at very low concentration (ca. 0.01 wt %, at room temperature). The blue color is accompanied by a structured absorption around 580-730 nm, which is characteristic of cobalt (II) in the tetrahedral (T_d) coordination. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) of the gel-like phase confirms the formation of networks of fibrous nanoassemblies with widths of 5-30 nm. The observed widths are larger than a molecular length of the triazole ligand (ca. 2.2 nm) and they are consisted of aggregates of T_d coordination polymers. Very interestingly, the blue gel-like phase turned into a solution by cooling below 25 ℃. A pale pink solution is obtained at 0 ℃, indicating the formation of octahedral (O_h) complexes. The observed thermochromic transition is totally reversible. The formation of gel-like networks by heating is contrary to the conventional organogels, which dissolve upon heating. Temperature dependence of the storage and loss moduli (G' and G") shows minima around at 27 ℃, at which temperature they gave comparable values. On the other hand, G' exceeds G" both in the gel-like phase (temperature above 27 ℃) and in the solution phase (temperature below 25 ℃). These observations indicate that T_d complexes are present as low-molecular weight species around at 25-27 ℃. They are self-assembled to polymeric T_d complexes by heating and form gel-like networks. Upon cooling the solution below 25 ℃, T_d complexes are converted to O_h complexes and they also self-assemble into oligomeric or polymeric species at lower temperatures. The observed unique thermochromic transition (pink solution → blue gel-like phase) is accompanied by an exothermic peak in differential scanning calorimetry (DSC), and is shown to be an enthalpy-driven process. The lipophilic modification of one-dimensional coordination systems provides unique solution properties and it would be widely applicable to the design of thermoresponsive, self-assembling molecular wires.