Phase Separation in Liquid Crystalline Mesophases of [Co(H2O)6]X2:P65 Systems (X = NO3-, Cl-, or ClO4-)

Abstract

Transition-metal aqua complex salts [M(H2O)6]X 2 (where M is Mn(II), Co(II), Ni(II), Zn(II), or Cd(II) and X is NO3-, Cl-, or ClO4-) can be dissolved in triblock poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) copolymers (Pluronics, such as P65) to form homogeneous liquid crystalline (LC) mesophases. However, the [Co-(H2O) 6]X2:P65 LC mesophases slowly undergo phase separation into a disordered ion-free phase and an ordered ion-rich LC mesophase. The phase separation also takes place in the two-salt systems [Co(H2O) 6](NO3):[Co(H2O)6]-(ClO 4)2:P65 in which the ion-free disordered domains separate out from the initially ordered homogeneous mesophase. The phase separation results in a physical mixture of a hexagonal nitrate-rich and cubic perchlorate-rich LC and disordered ion-free domains in the mixed salt systems. The driving force in the phase separation in the [Co(H2O) 6]-X2:P65 system is Co(II)-catalyzed aerobic oxidation of P65 into ester and/or other oxidation products. The separation of ions in the [Co(H2O)6](NO3)2:[Co(H 2O)6](ClO4)2:P65 system is related to the mesostructures of the two-salt systems that are different, hexagonal in the [Co(H2O)6](NO3)2:P65 system and cubic in the [Co(H2O)6](ClO4)2:P65 system. There is no visible phase separation in the other transition-metal salt:P65 systems. The phase separation in the [Co-(H2O) 6]X2:P65 systems can also be eliminated by keeping the mesophase under a N2 atmosphere. © 2007 American Chemical Society