Multicomponent Self-Assembly of a Giant Heterometallic Polyoxotungstate Supercluster with Antitumor Activity.

The hierarchical aggregation of molecular nanostructures from multiple components is a grand synthetic challenge, which requires highly selective linkage control. We demonstrate how two orthogonal linkage groups, that is, organotin and lanthanide cations, can be used to drive the aggregation of a giant molecular metal oxide superstructure. The title compound {[(Sn(CH ) ) O] {[CeW O ] [TeW O ][CeSn(CH ) ] [TeW O ] } } (1 a) features dimensions of ca.

Engineering polyoxometalate-intercalated layered double hydroxides for catalytic applications.

Polyoxometalate-intercalated layered double hydroxide (POM-LDH) nanocomposites have received considerable attention in recent years because such nanocomposites not only inherit the intrinsic properties of POMs and LDHs but also exert significant synergistic effects during the catalytic process. In this frontier article, we present the latest advances on the POM-LDH nanocomposites ranging from new synthetic methods to catalytic applications. By making use of the host layer modification method and exfoliation assembly method, the as-prepared POM-LDH nanocomposites show a wide range of catalytic applications.

1-D Chain Tungstotellurate Hybrids Constructed from Organic-Ligand-Connecting Iron-Lanthanide Heterometal Encapsulated Tetrameric Polyoxotungstate Units.

A family of inorganic-organic hybrid one-dimensional (1-D) chain iron-lanthanide (Ln) heterometal encapsulated tungstotellurates [HN(CH)]KNa[Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)][Ln(HO)Fe(Hpdca)(B-β-TeWO)]·50HO [Ln = Eu (), Tb (), Dy (), Er (), HAc = acetate acid, Hpdca = 2,5-pyridinedicarboxylic acid] were prepared using a facile "one-pot" reaction. The molecular structures of - consist of an intriguing organic-ligand-connecting Fe-Ln heterometal inserted tetrameric unit [Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)][Ln(HO)Fe(Hpdca)(B-β-TeWO)]. Appealingly, the tetrameric unit is composed of two sandwich-type subunits [Ln(Ac)(HO)Fe(Hpdca)(B-β-TeWO)] and [Ln(HO)Fe(Hpdca)(B-β-TeWO)], in which each sandwich-type subunit can be regarded as a derivative of two Ln-organic complexes substituting two external Fe ions in the classic Krebs-type [Fe(HO)(β-TeWO)] fragment.

Aggregation of Giant Cerium-Bismuth Tungstate Clusters into a 3D Porous Framework with High Proton Conductivity.

The exploration of high nuclearity molecular metal oxide clusters and their reactivity is a challenge for chemistry and materials science. Herein, we report an unprecedented giant molecular cerium-bismuth tungstate superstructure formed by self-assembly from simple metal oxide precursors in aqueous solution. The compound, {[W Ce O ]([W Bi Ce (H O) O ][B-α-BiW O ] ) } was identified by single-crystal X-ray diffraction and features 104 metal centers, a relative molar mass of ca.

Rare-Earth-Incorporated Tellurotungstate Hybrids Functionalized by 2-Picolinic Acid Ligands: Syntheses, Structures, and Properties.

A series of organic-inorganic rare-earth-incorporated tellurotungstate hybrids, Na[RE(HO)(pica)WO][(RE(HO)W(Hpica)O)(B-β-TeWOH)]·38HO (RE = La (1), Ce (2), Nd (3), Sm (4), Eu (5); Hpica = 2-picolinic acid), were prepared via a one-step assembly reaction of NaWO·2HO, RE(NO)·6HO, KTeO, Hpica, and triethylamine (tea). Notably, the solubilization of tea toward Hpica and the solubilization of Hpica toward RE cations in the reaction system play an important role in the formation of 1-5. The most significant feature of 1-5 consists of an intriguing tetrameric [RE(HO)(pica)WO][(RE(HO)W(Hpica)O)(B-β-TeWOH)] polyoxoanion constructed from two tetravacant Keggin sandwich-type [(RE(HO)W(Hpica)O)(B-β-TeWOH)] entities linked by a RE-W-Hpica {RE(HO)(pica)WO} cluster, in which Hpica ligands not only play a key bridging role in linking RE and W centers by carboxylic groups in an irregular N-O-RE-O-W-O six-membered-ring motif but also can directly chelate with W centers via N and O atoms in a stable N-O-C-O-W five-membered-ring fashion.

Tellurotungstate-Based Organotin-Rare-Earth Heterometallic Hybrids with Four Organic Components.

A family of unprecedented tellurotungstate-based organotin-rare-earth (RE) heterometallic hybrids [HN(CH)]HNa {[Sn(CH)WO(IN)][(B-α-TeWO)RE(HO) (Ac)]}·25HO [RE = Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7); HIN = isonicotinic acid, HAc = acetic acid] were synthesized and characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric analyses, powder X-ray diffraction, and single-crystal X-ray diffraction. The polyoxoanionic skeletons {[Sn(CH)WO(IN)][(B-α-TeWO)RE(HO) (Ac)]} of 1-7 are constructed from two symmetrical units {[Sn(CH)WO(IN)][(B-α-TeWO)RE(HO) (Ac)]} linked by two acetate connectors, which not only represent the first inorganic-organic hybrid RE-substituted tellurotungstates involving three different organic ligands, but also stand for the first samples of organotin-RE heterometallic polyoxometalate derivatives. The solid-state luminescent emission properties of 2-5 mainly display the characteristic emission bands of RE cations, whereas during the emission procedure of 7, [B-α-TeWO] segments make a nonignorable contribution to the PL behavior of 7 accompanying by the occurrence of the intramolecular energy transfer from O→W LMCT energy to Tb centers.