Designed Synthesis of POM–Organic Frameworks from {Ni₆PW₉} Building Blocks under Hydrothermal Conditions

Abstract

Die direkte Kombination von {Ni6PW9}‐Baugruppen mit starren Carboxylatbrücken unter Hydrothermalbedingungen führt zu Polyoxometallat‐organischen Netzwerken (POMOFs) mit 1D‐, 2D‐ und 3D‐Strukturen auf der Grundlage von Monomeren, Dimeren oder helikalen Ketten (siehe Bild einer 3D‐Struktur; WO6 rot, NiO6 grün, PO4 gelb, 1,2,4‐Benzoltricarboxylat gold).

A Series of Vanadogermanates from 1D Chain to 3D Framework Built by Ge–V–O Clusters and Transition‐Metal‐Complex Bridges

“…However, few investigations have been carried out on TM-substituted POVs because it is hard to obtain lacunary POV precursors, compared with abundant TM-substituted polyoxotungstates. [14] Therefore, we initiated an exploration of the As-V-O synthetic system in the presence of second TM ions under hydrothermal conditions with the aim of obtaining TM-substituted POVs. Accordingly, we have successfully made a series of mono-and di-TM-substituted As-V-O clusters (TM = Ni, Zn, Cd).…”

Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)4S6], [(RSn)3S4]2−, [(RT)2(CuPPh3)6S6], and [(RSn)6(OMe)6Cu2S6]4− (R=C2H4COOH, CMe2CH2COMe; T=Ge, Sn)

“…However, instead of a coupling of functionalized, polynuclear chalcogenidometallate clusters, networks of amine-linked clusters were generated lately based on solvothermal reactions of main group chalcogenide clusters in the presence of amines 4,4-trimethylenedipyridine, [10] similar to the synthesis of POM-organic networks from heteropolytungstate anions by bicarboxylic acids under hydrothermal conditions. [11] To contribute to a directed route into metalchalcogenideorganic frameworks we are currently investigating possible candidates for derivatization and functionalization of chalcogenidometallate complexes, starting out from adamantaneAbstract: A series of compounds comprising functionalized thiometallate cages [(RT) 4 S 6 ] (R terminated by COO(H) or COR groups), based on adamantane (T = Ge) or double-decker (T = Sn) type structures or [(RSn) 3 S 4 ] 2À anionic defect heterocubanes were synthesized and their reactions with 1) transition-metal compounds and 2) hydrazine derivatives were explored. Hence it was possible to generate functionalized ternary CuSnS or CuGeS clusters and to transfer COR ligands into CRA C H T U N G T R E N N U N G (N-NH 2 ) or CRA C H T U N G T R E N N U N G (N-NHPh) terminal groups, respectively.…”

A banana-shaped iron(III)-substituted tungstogermanate containing two types of lacunary polyoxometalate units

“…Such isomerization from A-a-GeW 9 O 34 to B-a-GeW 9 O 34 has previously been observed under the conventional aqueous solution conditions and hydrothermal conditions [12,23]. Although the degradation from XW 9 O 34 to XW 6 O 16 was observed under the conventional aqueous solution conditions [34], such degradation is first discovered under hydrothermal conditions.…”

“…Laterly, we initiate the investigation on the reactivity of the trivacant XW 9 O 34 precursors with electrophilic TM ions under hydrothermal conditions. A series of novel high-nuclear TMSPs are successfully isolated [8][9][10][11][12]. As our continuous work, we obtain a banana-shaped iron(III)-substituted tungstogermanate (H 2 en) 2 [29].…”