Anderson-Type Heteropolymolybdates Containing Tris(alkoxo) Ligands: Synthesis and Structural Characterization

Hasenknopf, Bernold; Delmont, Renaud; Herson, Patrick; Gouzerh, Pierre

doi:10.1002/1099-0682(200205)2002:5<1081::aid-ejic1081>3.0.co;2-w

Cited by 189 publications

(176 citation statements)

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“…The tris-ligands can be synthesized first and then be grafted onto the POM (pre-functionalization) or trisligands can further be modified by organic reactions after attachment onto the POM (postfunctionalization) [85]. They may cap either a tetrahedral cavity by connecting to two μ 3 -O atoms and one μ 2 -O atom (χ-isomer, Figure 4A) or by capping the templating heteroatom and connecting to three μ 3 -O atoms (δ-isomer, Figure 4B) [86]. Due to the rather high symmetry of the inorganic Anderson-Evans POM and the presence of protonated μ 3 -O atoms on both sides of the planar structure, functionalization with tris-ligands naturally results in double-sided products ( Figure 4C) but both isomers can be synthesized single-sided ( Figure 4A-B) too (see section 4.2.2).…”

Section: Topology Of "Extended"organic-inorganic and Tris-functionalimentioning

confidence: 99%

“…Combined ball-and-stick and polyhedral representation of single-sided χ-isomer (A), single-sided δ-isomer (B) and double-sided δ-isomer (C). Red octahedra: Mo; green octahedra: heteroatom in a low oxidation state; black spheres: C; blue spheres: N; red spheres: O; grey sphere: H. Figure 5 shows the periodic table and highlights heteroatoms that have been functionalized with trisligands [86]. All known tris-functionalized systems are in the XMo 6 system with the majority of the reported structures containing Mn III or Cr III heteroatoms.…”

Section: Page 8 Of 44mentioning

confidence: 99%

“…In 2002 Hasenknopf et al [86] reported the [MnMo 6 O 18 {(OCH 2 ) 3 CNO 2 } 2 ] 3-anion, which was the first ever report of a tris-functionalized Anderson-Evans POMs. The compound was obtained by refluxing acetylacetonate or acetate salts of the templating heteroatom (Mn III ) together with [TBA] 4 [α- Mo 8 O 26 ] and tris-NO 2 in acetonitrile (Figure 7, A1).…”

Section: Synthesis Of Tris-functionalized δ-Isomers By Re-arrangementmentioning

confidence: 99%

“…The compound was obtained by refluxing acetylacetonate or acetate salts of the templating heteroatom (Mn III ) together with [TBA] 4 [α- Mo 8 O 26 ] and tris-NO 2 in acetonitrile (Figure 7, A1). The six protons on the μ 3 -O atoms surrounding the Mn III heteroatom on both sides are replaced by the tris-ligands giving the δ-isomer ( Figure 4B) [86]. Rosnes et al [178] showed that both isomers [α-Mo 8 [179,180] can be used to synthesize hybrid organic-inorganic Mn III Mo 6 compounds.…”

Section: Synthesis Of Tris-functionalized δ-Isomers By Re-arrangementmentioning

confidence: 99%

See 3 more Smart Citations

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

Blazevic

Rompel

2016

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Section: Topology Of "Extended"organic-inorganic and Tris-functionalimentioning

confidence: 99%

Section: Page 8 Of 44mentioning

confidence: 99%

Section: Synthesis Of Tris-functionalized δ-Isomers By Re-arrangementmentioning

confidence: 99%

Section: Synthesis Of Tris-functionalized δ-Isomers By Re-arrangementmentioning

confidence: 99%

See 2 more Smart Citations

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

Blazevic

Rompel

2016

Coordination Chemistry Reviews

282

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“…71 (Figures 1b and 1c). The amido-pyridyl tris-alkoxo MnAnderson (POM-1) has been reported previously 76 and shown to assemble into a gel upon addition of Pd 2+ , 78 but the amide group introduces a kink in the linear geometry, so POM-2 was prepared as an alternative, linear linker, which is closely related in size and geometry to the well- Figure 1d). 79 Both POMs were isolated as tris tetra-n-butylammonium (TBA) salts, for superior solubility in organic solvents.…”

Section: Introductionmentioning

confidence: 96%

Synthetic Considerations in the Self-Assembly of Coordination Polymers of Pyridine-Functionalized Hybrid Mn-Anderson Polyoxometalates

Yazigi

Wilson

Long

et al. 2017

Crystal Growth & Design

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The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs such as metal-organic frameworks (MOFs) is desirable for a range of applications where intrinsic properties inherited from both the MOF and POM are utilised, including catalysis and magnetic data storage. The controlled self-assembly of targeted MOF topologies containing POM units is hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as coordinating groups towards linking metal cations leading to a diverse range of structures, but incorporation of organic donor units into hybrid POMs offers an alternative methodology to programmably synthesise POM/MOF conjugates. Herein, we report six coordination polymers obtained serendipitously wherein Zn 2+ and Cu 2+ link pyridine-appended Mn-Anderson clusters into two-and three-dimensional network solids with complex connectivities and topologies.2 Careful inspection of their solid-state structures has allowed us to identify common structuredirecting features across these coordination polymers, including a square motif where two Zn 2+ cations bridge two POMs. By correlating certain structural motifs with synthetic conditions we have formulated a series of design considerations for the self-assembly of coordination polymers of hybrid POMs, encompassing the selection of reaction conditions, co-ligands and linking metal cations. We anticipate that these synthetic guidelines will inform the future assembly of hybrid POMs into functional MOF materials. INTRODUCTIONPolyoxometalates ( ) that have been widely studied for their catalytic, [4][5][6][7][8][9] magnetic, 10-17 photochromic 18-21 and redox properties. [22][23][24][25][26][27][28] Given their large range of their chemical and physical properties, their incorporation into Metal-Organic Frameworks (MOFs) -network structures composed of metal clusters or metal ions connected by organic linkers -or more generally into porous frameworks has been investigated. 29,30 Creating POM/MOF conjugate materials can associate their individual properties, for instance the catalytic properties of a POM with the large surface area of a MOF, 31 or achieving a synergistic effect, for example the cooperative effect of single molecule magnets 32 or enhanced photocatalytic proton reduction. 33 To do so, two main approaches have been followed to date ( Figure 1a). The first is the impregnation of the POMs into the pores of a MOF, where POMs are either added during the MOF synthesis and trapped in the pores, [34][35][36][37][38][39][40] or they are inserted postsynthetically by soaking the MOF in a solution of the desired POM. [41][42][43][44] The second approach is to consider POMs as building blocks for porous structures, 45 with the aim of creating a bond between the POM and 3 either an organic linker (usually a multitopic carboxylic acid or N-donor ligand) [46][47][48][49] -di-(4-pyridyl)-1,4,5,8- (Figures 1b and 1c). The amido-pyridyl tris-alkoxo MnAnderson (POM-1) has been reported previously 76 and sh...

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Highly Efficient Peptide Bond Formation to Functionalized Wells‐Dawson‐Type Polyoxotungstates

et al. 2003

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Polyoxometalates (POMs) are a large family of metal-oxygen clusters of the early transition metals in high oxidation states, most commonly V V , Mo VI , and W VI . [1,2] Their diversity in structure and composition allows a wide versatility in terms of shape, polarity, redox potentials, surface charge distribution, and acidity. The last twenty years have witnessed a growing interest in the biological properties of POMs and their potential applications in medicine.[3] POMs exhibit antiviralnotably anti HIV [4,5] -as well as antitumor [6,7] and antibiotic [8,9] activities. Nonetheless, progress along these lines has been quite slow because of the low physiological stability of most POMs. Only a few POMs were reported with enhanced hydrolytic stability. [4,10,11] An original approach is the encapsulation of POMs in starch nanoparticles. [6] The introduction of organic groups into the POM framework could greatly increase the number of compounds available for screening, together with a potential modulation of essential features, such as stability, bioavailability, and recognition.[3] While there is a significant amount of work on hybrid POMs, [12][13][14] there have been only scattered reports of the reactivity of the side chain of such functionalized POMs. [15][16][17] Many of these organically derivatized POMs are unstable in water. Starting from hydrolytically more stable cyclopentadienyltitanium substituted POMs, [11,18] Keana reported the preparation and reactivity of derivatives with various functional groups. [19][20][21] We decided to reexamine the heteropolytungstates [a 2 -P 2 W 17 O 61 (SnR)] 7À reported by Pope and co-workers, [22,23] with an alkyltin group in place of the more fragile CpTi-moiety. These heteropolytungstate compounds have promising antitumor activities, [24] but the organic groups that were introduced were very simple and did not allow further functionalization. [18,22,24] It is important to have access to a wide variety of organic groups on the POM to meet specific requirements in biological applications. Different groups will enable the POM, for instance, to cross a membrane or to reach a specific receptor depending on their precise nature. We report herein our first findings on a flexible synthetic approach.To . [22,24] This strategy suffers from the incompatibility of the trichlorotin moiety with most organic functions, and the scarce versatility it allows. To prepare a functionalized POM useful as a scaffold for many applications, we decided to graft a pendant carboxylic acid onto a POM (Scheme 1), because it would allow peptide or ester coupling reactions, which are compatible with most bioactive compounds.The treatment of a buffered aqueous solution of K 10 [a 2 -P 2 W 17 O 61 ] 2 [25] with Cl 3 Sn(CH 2 ) 2 CO 2 H 7[26] yielded a new anion which was precipitated by the addition of nBu 4 NBr. The IR spectrum shows the vibrational bands arising from the Wells-Dawson structure without the typical splitting of the PÀO stretching vibration in the lacunary compound, [27] thus indicating t...

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Anderson-Type Heteropolymolybdates Containing Tris(alkoxo) Ligands: Synthesis and Structural Characterization

Cited by 189 publications

References 18 publications

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

Synthetic Considerations in the Self-Assembly of Coordination Polymers of Pyridine-Functionalized Hybrid Mn-Anderson Polyoxometalates

Highly Efficient Peptide Bond Formation to Functionalized Wells‐Dawson‐Type Polyoxotungstates

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