From chemistry to materials, design and photophysics of functional terbium molecular hybrids from assembling covalent chromophore to alkoxysilanes through hydrogen transfer addition

Two silica-based organic-inorganic hybrid materials composed of phenol (PHE) and ethyl-p-hydroxybenzoate derivatives (abbreviated as EPHBA) complexes were prepared via a sol-gel process. The active hydroxyl groups of PHE/EPHBA grafted by 3-(triethoxysilyl)-propyl isocyanate (TESPIC) through hydrogen transfer reaction were used as multi-functional bridged components, which can coordinate to Tb3+ with carbonyl groups, strongly absorb ultraviolet and effectively transfer energy to Tb3+ through their triplet excited state, as well as undergo polymerization or crosslinking reactions with tetraethoxysilane (TEOS), for anchoring terbium ions to the silica backbone. For comparison, two doped hybrid materials in which rare-earth complexes were just encapsulated in silica-based sol-gel matrices were also prepared. NMR, FT-IR, UV/vis absorption and luminescence spectroscopy were used to investigate the obtained hybrid materials. UV excitation in the organic component resulted in strong green emission from Tb3+ ions due to an efficient ligand-to-metal energy transfer mechanism. - Graphical abstract: The active hydroxyl groups of phenol/ethyl-p-hydroxybenzoate grafted by 3-(triethoxysilyl)-propyl isocyanate (TESPIC) through hydrogen transfer reaction were used as multi-functional bridged components, which can coordinate to Tb3+ with carbonyl groups, strongly absorb ultraviolet and effectively transfer energy to Tb3+ through their triplet excited state, as well as undergo polymerization or crosslinking reactions with tetraethoxysilane (TEOS), for anchoring terbium ions to the silica backbone with covalently bonded