Preparation of spiroborate supramolecular and peapod polymers containing a photoluminescent ruthenium(ii) complex

Abstract

The immobilization of functional metal complexes onto polymer supports remains one of the most important research areas. In this study, we prepared spiroborate supramolecular and peapod polymers containing a cationic photoluminescent ruthenium(II) complex. The supramolecular polymer was obtained by mixing spiroborate cyclic trimer bearing homoallyl group and a ruthenium(II) tris(bipyridyl) complex, and was further converted into the corresponding peapod polymer by olefin metathesis polymerization. The structure of these polymers was determined by ¹H NMR, dynamic light scattering, inductively coupled plasma-atomic emission spectroscopy, energy dispersive X-ray analyses, and atomic force microscopy. The absorption and emission behaviors of the ruthenium(II) complex were almost the same for the free form and the supramolecular polymer in the mixed solvent of N,N-dimethylformamide and chloroform, although the emission intensity decreased when the chloroform portion was increased. On the other hand, the hypsochromism was observed upon the emission of the ruthenium(II) complex in the peapod polymer, probably due to the rigidochromic effect of the tight encapsulation by the peapod structure.