Ag(i)-mediated self-assembly of anisotropic rods and plates in the surfactant mixture of CTAB and Pluronics

Abstract

One-dimensional (1D) metallogels are commonly observed in metal-coordinated complexes, but there are not many examples of soft crystalline solids which are generated by the self-assembly of metal–polymer complexation in a non-gel state. In a continued effort to obtain 1D materials by utilizing the tendency of Pluronic triblock copolymers to be micellized anisotropically at an elevated temperature, we investigate Ag(I)-mediated self-assembly of the surfactant mixture of Pluronic copolymers and cetyltrimethylammonium bromide (CTAB). At sufficiently high temperature, Pluronic copolymers are known to organize into many crystalline mesophases, such as body-centered-cubic, hexagonal, and lamellar phases. Four Pluronics of L-31, L-64, P-123, and F-108 were studied, and at the concentration of 17.9%, macroscale 1D rods with the aspect ratios ranging from 3.07 to 12.8 are obtained. At the concentration of 35.7%, anisotropic two dimensional (2D) planar plates are observed. These planar structures were believed to be generated from 2D lamellar mesophases, which is consistent with the general phase diagram of Pluronic copolymers that shows lamellar phase with the highest concentration. In the absence of ascorbic acid, rods and plates of larger size are produced. Rather than as a reductant, ascorbic acid is thought to play the roles of an agent to increase the hydrophilicity, and as a mediator to determine the dimension of rods and plates by hindering the long range self-assembly of alkyl chains. Dehydration by the addition of AgNO₃, and the increase of hydrophobicity enable self-assembly of alkyl groups of CTAB and Pluronics and promote the formation of crystalline soft solids.