Hexavanadate–Organogold(I) Hybrid Compounds: Synthesis by the Azide–Alkyne Cycloaddition and Density Functional Theory Study of an Intriguing Electron Density Distribution

Petrovskii, S. K.; Khistiaeva, Viktoria; Sizova, Anastasia A.; Sizov, V. V.; Paderina, Aleksandra; Koshevoy, Igor O.; Monakhov, Kirill Yu.; Grachova, Elena V.

doi:10.1021/acs.inorgchem.0c02621

Cited by 16 publications

(24 citation statements)

References 29 publications

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“…For the reported stable electronic states, no effect of the R group on charge leakage is observed, which is different from the case when R bears a metalorganic moiety in such Lindqvist-type hexavanadates. 12 Importantly, the structural integrity of the studied POV6 core is preserved during electron uptake. Our calculations indicate that the highly stable configurations of POV6 with four to nine additional electrons offers opportunities in the fields of multi-bit data storage and batteries.…”

Section: Discussionmentioning

confidence: 99%

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What is the maximum charge uptake of Lindqvist-type polyoxovanadates in organic–inorganic heterostructures?

Sorokina

Ryndyk

Monakhov

et al. 2022

Phys. Chem. Chem. Phys.

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Section: Discussionmentioning

confidence: 99%

“…via azide-alkyne cycloaddition. 2,12 We show that the ideal setup does not depend on the type of the ligand R group, while the best electron capacity of up to 9 electrons can be achieved when applying hydrogen ions as charge-balancing entities for the bisligated POV6 core. Two types of calculations have been carried out.…”

Section: Introductionmentioning

confidence: 95%

What is the maximum charge uptake of Lindqvist-type polyoxovanadates in organic–inorganic heterostructures?

Sorokina

Ryndyk

Monakhov

et al. 2022

Phys. Chem. Chem. Phys.

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“…POMs are molecular metal oxide anions based on early transition metals such as Mo, V, and W. [4] Over recent years, the covalent functionalization of POMs with organic or metal complex groups has led to tremendous progress in functional organic‐inorganic hybrid materials. [ 5 , 6 , 7 , 8 , 9 ] This has led to breakthroughs in bioinorganic hybrids, [10] supramolecular nanostructures[ 11 , 12 , 13 ] and electrochemical surface functionalization. [14] …”

Section: Introductionmentioning

confidence: 99%

Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

Çetindere

Clausing

Anjass

et al. 2021

Chemistry A European J

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The covalent attachment of molecular photosensitizers (PS) to polyoxometalates (POMs) opens new pathways to PS‐POM dyads for light‐driven charge‐transfer and charge‐storage. Here, we report a synthetic route for the covalent linkage of BODIPY‐dyes to Anderson‐type polyoxomolybdates by using CLICK chemistry (i. e. copper‐catalyzed azide‐alkyne cycloaddition, CuAAC). Photophysical properties of the dyad were investigated by combined experimental and theoretical methods and highlight the role of both sub‐components for the charge‐separation properties. The study demonstrates how CLICK chemistry can be used for the versatile linkage of organic functional units to molecular metal oxide clusters.

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“…In fact, we could showcase it in the study of fully oxidized Lindqvist-type hexavanadates decorated with phosphine-derivatized Au(I) moieties. 52 The performed gas-phase DFT calculations on these hybrid compounds indicated a gradual shift of the electronic density from the central hexavanadate core to the organogold(I) fragments, with increasing number of unpaired electrons in the 3d orbitals of vanadium.…”

Section: Ion Soft-landing Of Mass-selected Pomsmentioning

confidence: 96%

“…This hinders quite effectively the agglomeration in solution and enables a homogeneous distribution of single molecules on surfaces by simple coating from the liquid phase. (ii) The hexavanadate structure can be chemically fine-tuned without change to the Lindqvist-type metal–oxo skeleton, for example, by heteroatoms , or organic − or organometallic ligands. This allows optimal tailoring for a specific operational field, for example, biochemistry and biomedicine…”

Section: Electronic Modification Of Poms On Surfacesmentioning

confidence: 99%

Insights from Adsorption and Electron Modification Studies of Polyoxometalates on Surfaces for Molecular Memory Applications

et al. 2021

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Metrics & More Article RecommendationsCONSPECTUS: 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 and are characterized by the excellent ability to change their redox states without significant structural distortions of the central polyoxoanion core, can be immobilized best and how they may work optimally at appropriate surfaces. Furthermore, we critically discuss important issues and challenges on the long way toward POM-based nanoelectronics. This Account is divided into four sections shedding light on POM interplay in solution and on surfaces, ion soft-landing of mass-selected POMs on surfaces, electronic modification of POMs on surfaces, and computational modeling of POMs on surfaces. The sections showcase the complex nature of far-reaching POM interactions with the chemical surroundings in solution and the properties of POMs in the macroscopic environment of electrode surfaces. Section 2 describes complex relationships of POMs with their counter-cations, solvent molecules, and water impurities, which have been shown to exhibit a direct impact on the resulting surface morphology, where a concentration-dependent formation of micellar structures can be potentially observed. Section 3 gives insights into the ion softlanding deposition of mass-selected POMs on electrode surfaces, which emerges as an appealing method because the simultaneous deposition of agglomeration-stimulating counter-cations can be avoided. Section 4 provides details of electronic properties of POMs and their modification by external electronic stimuli toward the development of multiple-state resistive (memristive) switches. Section 5 sheds light on issues of the determination of the electronic structure properties of POMs across their interfaces, which is difficult to address by experiment. The studies summarized in these four sections have employed various X-ray-scattering, microscopy, spectroscopy, and computational techniques for imaging of POM interfaces in solution and on surfaces to determine the adsorption type, agglomeration tendency, distribution, and oxidation state of deposited molecules. The presented research findings and conceptual ideas may assist experimentalists and theoreticians to advance the exploration of POM electrical conductivity as a function of metal redox and spin states and to pave the way for a realization of ("brain-inspired") POM-based memory devices, memristive POM-surface device engineering, and energy efficient nonvolatile data storage and processing technologies.

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Hexavanadate–Organogold(I) Hybrid Compounds: Synthesis by the Azide–Alkyne Cycloaddition and Density Functional Theory Study of an Intriguing Electron Density Distribution

Cited by 16 publications

References 29 publications

What is the maximum charge uptake of Lindqvist-type polyoxovanadates in organic–inorganic heterostructures?

What is the maximum charge uptake of Lindqvist-type polyoxovanadates in organic–inorganic heterostructures?

Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

Insights from Adsorption and Electron Modification Studies of Polyoxometalates on Surfaces for Molecular Memory Applications

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