Self-Organization and Swelling of Ruthenium-Metal Coordination Polymers with PTA (Metal = Ag, Au, Co).

ABSTRACT

We present the internal structure and dynamics of novel coordination polymers based on two metal-containing moieties Ru-X (X Ag, Au, Co), bridged through the phosphine PTA (3,5,7-triaza-phosphaadamantane). X-ray scattering gives the heterometallic polymer organization. Quasi-elastic neutron scattering measurements over a broad temperature range show a transition from vibrational Debye-Waller behavior to a more dynamically active state, but with rather localized motions, coinciding with the loss of structural water at around room temperature. Light scattering reveals that the polymers self-associate to form stable micro-particles in aqueous solution with a thermally driven volume transition. This is described by the Flory theory for polymers in solution, in which the polymer solvency is calculated as a function of the temperature. Polymer self-organization is further studied by small-angle neutron scattering and electron microscopy. A polymer parallel-plane model with gaps controlled by the environmental temperature is proposed.