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A series of rare earth metal amido complexes bearing methylene-linked pyrrolyl-amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent-free conditions for liquid substrates. Treatment of [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) with 2-(2,6-Me(2)C(6)H(3)NHCH(2))C(4)H(3)NH (1, 1 equiv) in toluene afforded the corresponding trivalent rare earth metal amides of formula {(μ-η(5):η(1)):η(1)-2-[(2,6-Me(2)C(6)H(3))NCH(2)](C(4)H(3)N)LnN(SiMe(3))(2)}(2) [Ln=Y (2), Nd (3), Sm (4), Dy (5), Yb (6)] in moderate to good yields. All compounds were fully characterized by spectroscopic methods and elemental analyses. The yttrium complex was also characterized by (1)H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single-crystal X-ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence of the rare earth metal amido complexes (0.1 mol%) afforded the products in high yields (up to 99%) at room temperature in short times of 5 to 10 min. Furthermore, the catalytic addition of diethyl phosphite to unactivated ketones also afforded the products in high yields of up to 99% with employment of low loadings (0.1 to 0.5 mol%) of the rare earth metal amido complexes at room temperature in short times of 20 min. The system works well for a wide range of unactivated aliphatic, aromatic or heteroaromatic ketones, especially for substituted benzophenones, giving the corresponding α-hydroxy diaryl phosphonates in moderate to high yields.

A series of highly thermally stable lanthanide metal-organic frameworks formulated as [Ln 2 (TATB) 2 (DMSO) 6 ] •DMF•DMSO•H 2 O [Ln = La (1), Ce (2), Pr (3), Sm (4), Eu (5)] and [Ln 2 (TATB) 2 (DMSO) 5 (CH 3 OH)]•DMF•DMSO •2H 2 O [Ln = Nd (6), Gd (7), Tb (8)] (TATB 3− = 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoate, DMF = N,N-dimethylformamide and DMSO = dimethylsulfoxide) have been successfully synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction, infrared (IR) spectroscopy, elemental analysis, thermogravimetric analyses (TGA) and powder X-ray diffraction (PXRD). Single crystal X-ray diffraction analysis reveals that all of the compounds are isomorphous, crystallize in the triclinic space group P ¯1 and exhibit two-dimensional (2D) (3,3)-connected layered structures with the Schläfli symbol {6 3 }. Solid-state photoluminescence measurement illustrates that compounds 5 and 8 exhibit remarkable red and green luminescence emissions with lifetimes at the millisecond scale, respectively, while complexes 3, 4, and 6 display characteristic luminescence emissions in the near-infrared region. With careful adjustment of the relative concentration of the doping Eu 3+ and Tb 3+ ions in the La 3+ complex, the color of the luminescence can be modulated, and white-light emitting materials can be successfully obtained.

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