Versatile precursor to metal complexes: The lithiated N-heterocyclic carbene derivative [Li(imino–imidide)(tmeda)] (imino–imidide=4-(2,6-diisopropylphenylimino)imidazol-2-ylidenide), obtained by deprotonation and lithiation of a mesoionic 4-aryliminoimidazolium, serves as versatile complexes with the anionic 4-aryliminoimidazolide salt metathesis. DFT calculations demonstrate that tuneable electronic steric factors substituent at Nexo imino function heterocycle dictate preferred site...

A novel N,N′-diphosphanyl-imidazol-2-ylidene acts as a stable, hybrid PCNHCP ligand for M2 or linear M3 (M = Cu, Ag, Au) arrays with metallophilic interactions.

The sustainable development of IT-systems requires a quest for novel concepts to address further miniaturization, performance improvement, and energy efficiency devices. realization these goals cannot be achieved without an appropriate functional material. Herein, we target the technologically important electron modification using single polyoxometalate (POM) molecules envisaged as smart successors materials that are implemented in today's complementary metal-oxide-semiconductor (CMOS)...

Polyoxovanadate anions immobilized on conducting substrates are promising candidates for molecule-based memory technologies. However, strong electronic interactions with the substrate and formation of larger agglomerates remain bottlenecks way to their technical application. We demonstrate that ion soft-landing mass selected cyclodextrin-functionalized hexavanadates enables deposition these host–guest complexes as single units surfaces without quaternary ammonium countercations from...

We report a chemically programmed design and the switching characteristics of functional metal–DNA-origami–polyoxometalate (POM) material obtained from solution-processed assembling biocompatible molecular precursors. The DNA origami is immobilized on gold surface via thiolate groups acts as carrier (ad-layer) structure, ensuring spatially controlled hybridization pre-defined six-helix bundle (6HB) positions with DNA-augmented, tris(alkoxo)-ligated Lindqvist-type polyoxovanadate (POV6)...

Polyoxometalates (POMs) have attracted much attention in the development of data storage devices with alternative nanophysics. Numerous studies can be found on their integration into charge-based and resistive types memory. However, question whether POM behaves as a molecular capacitor or memristor remains largely unexplored. In this Article, we clarify fundamental by placing individual electronic properties POMs context chemical technical environment. By control charge stabilization reduced...

A new strategy has been reported for loading of polyoxometalates into metal–organic frameworks. It grants access to bifunctional electrocatalysts hydrogen and oxygen evolution reactions.

Abstract A water‐soluble derivative of the polyoxovanadate {V 15 E 6 O 42 } (E=semimetal) archetype enables study cluster shell rearrangements driven by supramolecular interactions. reaction unique to E=Sb, induced exclusively ligand metathesis in peripheral [Ni(ethylenediamine) 3 ] 2+ counterions, results formation metastable α 1 * configurational isomer 14 Sb 8 type. Contrary all other architectures, this comprises an inward‐oriented vanadyl group and is ca. 50 12 kJ mol −1 higher energy...

This Account highlights recent experimental and theoretical work focusing on the development of polyoxometalates (POMs) as possible active switching units in what may be called "molecule-based memory cells". Herein, we critically discuss how multiply charged vanadium-containing POMs, which exhibit stable metal-oxo bonds are characterized by excellent ability to change their redox states without significant structural distortions central polyoxoanion core, can immobilized best they optimally...

Redox- and spin-active macrocyclic vanadyl( iv ) complexes polyoxovanadates( v have promising structural physicochemical characteristics for innovative bottom-up hybrid electronics.

Abstract The interplay between extraterrestrial, atmospheric, aqueous, interfacial, and hydrothermal processes is crucial for Earth's prebiotic chemistry. Volcanic terrains contain polyoxometalates (POMs). Some polyoxocuprates were identified as building blocks of fumarole minerals produced from high‐temperature gases. existence polyoxovanadate anions in acidified reducing volcanic aquifers cannot be excluded. At present, it can only speculated whether life arose around natural POM deposits...

Mononuclear alkyl N-heterocyclic carbene complexes of the type Fe(NHC)R2, NHC = SIPri, IPri, R CH2SiMe3, CH2C6H5, were prepared by alkylation "FeCl2(THF)1.5" with one equivalent per Fe MgR2, in presence NHC. Alkylation 0.5 equiv MgR2 under carefully controlled conditions gave Fe(NHC)(CH2SiMe3)Cl, IPri. Magnetic and computational studies structural determination X-ray diffraction reveal three-coordinate high-spin (S 2) complexes.

We describe the unique structural and electronic arrangement in heptanuclear polyiodobismuthate [Bi7I24]3– which displays striking similarities with Anderson-type structures found polyoxometalates. This main group element anion is part of complex [Bi(OAc)2(thf)4]3[Bi7I24] (1) has been characterized by X-ray crystallography. investigated structure, stability, bonding using relativistic dispersion-corrected density functional theory combination a quantitative energy decomposition electron...

This Concept article provides insights into the molecular design and construction aspects of polyoxocuprates (POCus), an emerging class polyoxometalate (POM)-like architectures featuring low-to-high nuclearity copper(II)-oxo/hydroxo skeletons. POCus have been identified to adopt structural principles classical POMs consisting early transition metals. Their potential afford motifs noble-metal-based is exploited. "Cross-structural topological transformation" introduced generalize skeletal...

Mixed-valence polyoxovanadates(IV/V) have emerged as one of the most intricate class supramolecular all-inorganic host species, able to encapsulate a wide variety smaller guest templates during their self-assembly formation process. As showcased herein, incorporation guests, though governed solely by ultra-weak electrostatic and van der Waals interactions, can cause drastic effects on electronic magnetic characteristics shell complex polyoxovanadate. We address question methodology for...

Starting from the new ligands bis(diphenylphosphino)(N-4-(methylthio)phenyl)amine (4, N(PPh2)2(p-C6H4)SMe) and its monosulfide derivative (Ph2P)N{P(S)Ph2}(p-C6H4)SMe (4·S), we have prepared characterized, including by X-ray crystallographic studies, their Ni(II) complexes [NiCl2{(Ph2P)2N(p-C6H4)SMe-P,P}] (5) [NiCl2{(Ph2P)N{P(S)Ph2}(p-C6H4)SMe-P,S}] (6), respectively. The bis-sulfide compound N{P(S)Ph2}2(p-C6H4)SMe (4·S2) was also structurally characterized. Computational studies showed that...

We describe the synthesis, structures, and magnetochemistry of new M4Cl4 cubane-type cobalt(II) nickel(II) complexes with formula [M(μ3-Cl)Cl(HL·S)]4 (1: M = Co; 2: Ni), where HL·S represents a pyridyl-alcohol-type ligand thioether functional group, introduced to allow subsequent binding Au surfaces. Dc ac magnetic susceptibility data 1 2 were modeled full spin Hamiltonian implemented in computational framework CONDON 2.0. Although both coordination clusters are isostructural, each their...

The understanding of the molecular state vanadium-oxo clusters (polyoxovanadates, POVs) in solution and on surface is a key to their target application catalysis as well electronics spintronics. We here report results combined experimental computational study behavior nucleophilic polyoxoanions [VIV10VV8O42(I)]5– charged balanced by Et4N+ water, one-phase organic N,N-dimethylformamid (DMF) or acetonitrile (MeCN), mixed MeCN–water, at hybrid liquid–surface interface. characteristics compound...

The [V6O13{(OCH2)3CCH2OCH2C[triple bond, length as m-dash]CH}2]2- with two terminal alkyne functionalities exhibits excellent reactivity towards (bio-)organic azides. designed synthetic protocol for the generation of triazol-modified Lindqvist hexavanadates grants access to bio-"clicked" polyoxometalates spectroscopically detectable 51V nuclei.

A series of {V12}-nuclearity polyoxovanadate cages covalently functionalized with one or sandwiched by two phthalocyaninato (Pc) lanthanide (Ln) moieties via V-O-Ln bonds were prepared and fully characterized for paramagnetic Ln = SmIII-ErIII diamagnetic LuIII, including YIII. The LnPc-functionalized {V12O32} oxidized vanadium centers in the ground state isolated as (nBu4N)3[HV12O32Cl(LnPc)] (nBu4N)2[HV12O32Cl(LnPc)2] compounds. As corroborated a combined experimental (EPR, DC AC SQUID,...