Molecular assembly and photophysical properties of covalently bonded rare earth polymeric hybrid materials phen–RE–MSMA (MS)

A new series of quaternary and ternary polymeric hybrid materials were assembled from 3-methacryloxypropyltrimethoxysilane (MS), methacrylic acid (MA), 1,10-phenanthroline (phen) and rare earth (Eu3+, Tb3+, and Dy3+) precursors. MS and MSMA (copolymer of MS and MA) behave as structural functional component to form the inorganic polymeric network or inorganic/organic polymeric host through the coordination to rare earth ions, while phen acts as the energy sensitizer for the luminescence of rare earth ions. Subsequently, six novel hybrid materials (phen–Eu(Tb, Dy)–MS, phen–Eu(Tb, Dy)–MSMA) were obtained, in which inorganic component is connected with polymer component through covalent bond. It was found that the introduction of organic polymer unit has influence on the microstructure and especially the luminescent properties of hybrid materials. The quantum efficiency of Eu hybrids was also studied. All these hybrids exhibit the characteristic luminescence of rare earth ions, which substantiates optimum energy match and effective intramolecular energy transfer between the triplet state energy of phen and emissive energy level of Eu3+, Tb3+ and Dy3+. It was worth pointing out that the quaternary hybrid materials (phen–Eu3+(Tb3+, Dy3+)–MSMA) with organic polymer unit (MA) present stronger luminescence intensities, longer lifetimes than those of ternary ones without MA (phen–Eu3+(Tb3+, Dy3+)–MS), suggesting the introduction of organic chain (MA) is beneficial for the photophysical property of hybrids.