Organic–inorganic hybrid rare earth complexes based on polymolybdates with intrinsic photosensitive properties

Abstract

A series of organic–inorganic hybrid rare earth complexes {[RE2(PO)2(H2O)10][H2Mo36O112(OH2)12(PO)4]}·5PO·2(CH3CN)·nH2O [n = 23–42, RE(III) = Nd(III), 1; Sm(III), 2; Eu(III), 3; Gd(III), 4; Dy(III), 5; Er(III), 6; Tm(III), 7; Yb(III), 8; Lu(III), 9; Y(III), 10; PO = piperidin-2-one] have been synthesized and fully characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectra, thermogravimetric analysis and UV-vis spectra. Structural analysis reveals that compounds 1-10 are isostructural and crystallize in the monoclinic P2(1)/n space group. Each compound contains a centrosymmetric anionic cluster [Mo36O112(OH2)12(PO)4](8-), which could be described as the derivative of [Mo36O112(OH2)16](8-) with four water molecules substituted by organic PO molecules. Each {Mo18} subunit connects with one RE(III) ion via its two terminal O atoms from two independent {MoO6} octahedra. The eight coordinated RE(III) ion with a distorted tetragonal antiprism coordination geometry is also surrounded by another six oxygen atoms, five of them from five water molecules and the final one from one PO molecule. Compounds 1-10 show considerable photosensitive behavior under visible light excitation. In addition, compound 3 exhibits three emission bands at 580, 595 and 617 nm in the solid state, which could be assigned to (5)D0→(7)F0, (5)D0→(7)F1 and (5)D0→(7)F2 transitions of Eu(III) ions, respectively.

Carbonate-Bridged Lanthanoid Triangles: Single-Molecule Magnet Behavior, Inelastic Neutron Scattering, and Ab Initio Studies

“…which is consistent with literature reports of carbonate ligand decomposition in the range 460−480 °C for related [{RE-(OH 2 )} 3 CO 3 (A-α-XW 9 O 3 4 ) 2 ] n − and similar complexes 27,32,34,35. The 2-Y and 2-Er samples exhibit almost identical profiles, with around 4% mass loss attributed to hydrate molecules.…”

Missing Link in the Homologous Series of Lactams: The X-ray Structure of Valerolactam

“…So far, the molecular structure of 1 has only been described in respective co-crystals [25][26][27][28][29][30][31] and metal complexes. [32][33][34][35][36] Here, we describe for the first time a crystal structure of valerolactam (1) in the absence of other ligands, completing a homologous structural series of small and medium-sized lactams. After some difficulties we were able to determine the molecular structure of 1 from commercially available valerolactam.…”

“…Moreover, 1 is a valuable precursor for the total synthesis of different natural products − and is frequently employed in the development of chemical methodologies. − Additionally, several bioactive compounds are valerolactam derivatives. − Only recently, the biotechnological production of valerolactam ( 1 ) and a lactam biosensor have been introduced. So far, the molecular structure of 1 has been described in only respective cocrystals − and metal complexes. − Here, we describe for the first time a crystal structure of valerolactam ( 1 ) in the absence of other ligands, completing a homologous structural series of small- and medium-sized lactams.…”

Highly Stable Copper(I)-Based Metal–Organic Framework Assembled with Resorcin[4]arene and Polyoxometalate for Efficient Heterogeneous Catalysis of Azide–Alkyne “Click” Reaction

“…MOFs as an emerging functional material exhibit great promise in the fields of gas storage, molecular sensing, separation, electronics, and catalysis, among others. − In this facet, the versatility in the active sites of the MOFs has resulted in their applications in various sectors of catalysis, such as Brønsted acid and Lewis acid catalysis, photocatalysis, oxidations, hydrogenations, and asymmetrical catalysis et al − Nevertheless, a plenty of MOFs usually show the relatively low stability, which limits their further potential applications in catalysis. Alternatively, the introduction of POMs into the MOFs at the molecular level provides a promising way to possibly increase their stability. − …”

“…POMs into the MOFs at the molecular level provides a promising way to possibly increase their stability 43…”