Molecular design and photo-physics of quaternary hybrid terbium centered systems with novel functional di-urea linkages of strong chemical bonds through hydrogen transfer addition

Two kinds of crosslinking reagents, 3-aminopropyl-methyl-diethoxylsiliane (H2N(CH2)3SiCH3(OC2H5)2, abbreviated as APMES) and N-2-aminoethyl-3-aminopropyltriethoxylsiliane (H2N(CH2)2HN(CH2)3Si(OC2H5)3, abbreviated as AEAPES) are modified by 3-(triethoxysilyl)-propyl isocyanate (TESPIC) to afford two novel crosslinking molecular derivatives as bridge ligands. Then the ternary organic–inorganic molecular-based hybrid system with these functional bridge ligands and 1,10-phenanthroline (phen) are constructed with the two components equipped with covalent bonds. The two components of APMES (or AEAPES) and TESPIC is linked through –NHC(O)NH– groups which is applied to coordinate to Tb3+ and further formed Si–O backbones after co-hydrolysis and co-polycondensation processes, while phen behaves as the main energy donor for the sensitization of luminescence of Tb3+. Luminescence spectra were utilized to characterize the photo-physical properties of the obtained hybrid system and the above spectroscopic data reveal that the phen in this favorable hybrid system behaves the main energy donor for the luminescence of Tb3+. In this way, the intra-molecular energy transfer process took place within these molecular-based hybrids and strong green and blue emissions of Tb3+ have been achieved.

Graphical abstractTwo kinds of crosslinking reagents, 3-aminopropyl-methyl-diethoxylsiliane (H2N(CH2)3SiCH3(OC2H5)2, abbreviated as APMES) and N-2-aminoethyl-3-aminopropyltriethoxylsiliane (H2N(CH2)2HN(CH2)3Si(OC2H5)3, abbreviated as AEAPES) are modified by 3-(triethoxysilyl)-propyl isocyanate (TEPIC) to afford two novel crosslinking molecular derivatives as bridge ligands. Then the ternary and quaternary organic–inorganic molecular-based hybrid material with these functional and bridge ligands and 1,10-phenanthroline (phen) are constructed with the two components equipped with covalent bonds are reported.Figure optionsDownload full-size imageDownload as PowerPoint slide