The crystallisation of polyoxo-molybdate and -tungstate anions with phenylated phosphonium and arsonium cations, in relation to the crystal packing and species in solution

Alyea, Elmer C.; Craig, Don; Dance, Ian G.; Fisher, Karen R.; Willett, Gary D.; Scudder, Marcia L.

doi:10.1039/b505992e

Cited by 22 publications

(12 citation statements)

References 30 publications

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“…As we know,t he dichromate ion is aw ell-recognized species, however,i ts congener dimolybdate is not ac ommon species, having only been found in af ew coordination compounds. [18] The two equivalent O3 groupings in the Mo 2 O 7 2À anion of compound 4 are oriented essentially perpendicular to their re-spectiveM o ÀOb onds in as taggeredc onformation. The Mo1-O2-Mo1Aa ngle is perfectly 1808 imposed by an inversion center and the torsion angle of the Mo1-O1-O1 A-Mo1A moiety is 608 imposed by a3-fold axis, giving the Mo 2 O 7 2À ion aperfect D 3d symmetry.T he Mo 2 O 7 2À ion in compound 4 adopts a m 6k 1 :k 1 :k 1 :k 1 :k 1 :k 1 mode to dimerize two Ag 9 prisms to an Ag 18 cluster.T he AgÀO dimolybdate bond length (2.611 (9) ) is comparable to the AgÀO trifluoromethanesulfonate bond length.…”

Section: X-ray Structures and Assembly Discussionmentioning

confidence: 91%

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

Zhou

et al. 2016

Chemistry A European J

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A general class of C3 -symmetric Ag9 clusters, [Ag9 S(tBuC6 H4 S)6 (dpph)3 (CF3 SO3 )] (1), [Ag9 (tBuC6 H4 S)6 (dpph)3 (CF3 SO3 )2 ]⋅CF3 SO3 (2), [Ag9 (tBuC6 H4 S)6 (dpph)3 (NO3 )2 ] ⋅NO3 (3), and [Ag9 (tBuC6 H4 S)7 (dpph)3 (Mo2 O7 )0.5 ]2 ⋅2 CF3 COO (4) (dpph=1,6-bis(diphenylphosphino)hexane), with a twisted trigonal-prism geometry was isolated by the reaction of polymeric {(HNEt3 )2 [Ag10 (tBuC6 H4 S)12 ]}n , 1,6-bis(diphenylphosphino)hexane, and various silver salts under solvothermal conditions. The structures consist of discrete clusters constructed from a girdling Ag9 twisted trigonal prism with the top and bottom trigonal faces capped by diverse anions (i.e., S(2-) and CF3 SO3 (-) for compound 1, 2×CF3 SO3 (-) for compound 2, 2×NO3 (-) for compound 3, and tBuC6 H4 S(-) and Mo2 O7 (2-) for compound 4). This trigonal prism is bisected by another shrunken Ag3 trigon at its waist position. Interestingly, two inversion-related Ag9 trigonal-prismatic clusters are dimerized by the Mo2 O7 (2-) ion in compound 4. The twist is amplified by the bulkier thiolate, which also introduces high steric-hindrance for the capping ligand, that is, the longer dpph ligand. Four more silver-sulfur clusters (namely, compounds 5-8) with their nuclearity ranging from 6-10 were solely characterized by single-crystal X-ray diffraction to verify the above-described synergetic effect of mixed ligands in the construction of Ag9 twisted trigonal prisms. Surprisingly, only cluster 1 emits yellow luminescence at λ=584 nm at room temperature, which may be attributed to a charge transfer from the S 3p orbital to the Ag 5s orbital, or mixed with metal-centered (MC) d(10) →d(9) s(1) transitions. Upon cooling from 300 to 80 K, the emission intensity was enhanced along with a hypsochromic shift. The good linear relationship between the maximum emission intensity and the temperature for compound 1 in the range of 180-300 K indicates that this is a promising molecular luminescent thermometer. Furthermore, cyclic voltammetric studies indicated that the diffusion- and surface-controlled redox processes were determined for compounds 1 and 3 as well as compound 4, respectively.

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Section: X-ray Structures and Assembly Discussionmentioning

confidence: 91%

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

Zhou

et al. 2016

Chemistry A European J

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“…The tetrahedral stereochemistry of Ph 4 E requires that the chain is zig-zag, and this tertiary motif has been named the zig-zag sixfold phenyl embrace [8]. This motif occurs in a large number of crystals containing the Ph 4 P þ cation, and one example, (Ph 4 P þ ) 2 [Mo 6 O 19 ] 2À (CH 3 CN) 2 [9], is shown in Figure 5…”

Section: Intermolecular Embraces and Energies 271mentioning

confidence: 97%

Intermolecular Embraces and Intermolecular Energies

Dance

2005

Molecular Crystals and Liquid Crystals

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Control of the assembly of molecules in the crystalline state requires management of all possible intermolecular interactions, and their energies. Any one molecule is surrounded by and interacts with parts of the surface of several others, and it is the balance of all the intermolecular interaction energies that determines the lattice enthalpy, and therefore the product structure. In this context of competition between different intermolecular contacts, simplification occurs when intermolecular motifs operate in concert, as in multiple aryl embraces. Structural hierarchies of extended embrace motifs occur in crystals, analogous to the secondary ) tertiary ) quaternary construction of biological macromolecules. Some principles for the analysis and interpretation of intermolecular space in crystals are discussed.Richly abundant data on the packing of molecules in crystals provides the basis for the description of intermolecular motifs, but this data is only geometrical. A different property, intermolecular energy, is determinative in the assembly of molecules. In strong contrast to the abundance of geometrical data, there is a serious scarcity of experimental thermodynamic data about many types of intermolecular motifs, including embraces. However, intermolecular potentials for chemically diverse systems can be calculated efficiently by appropriate density functional methods. Key concepts relating intermolecular potentials, the van der Waals distance criterion, and distributions of intermolecular distances, are reiterated. Charged polyatomic molecules, prevalent in coordination chemistry, raise significant questions about the relative magnitudes and influences of the additional electrostatic components of intermolecular energy. Some of the issues and uncertainties in this, for instance in the multiple phenyl embraces that occur between homocharged molecules, are discussed.

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“…14 It is known that multiple phenyl embraces formed by arylated cations, such as Ph 4 P + , have a key influence on favourable crystallization of the [Mo 6 O 19 ] 2À anion due to the formation of chains of the embracing cations that surround columns of the polyoxometalate anions. 15 Therefore, a reasonable approach toward the synthesis of hybrids based on the Lindqvist Mo 6 O 19 2À anion lies in the suitable choice of counter cations.…”

Section: Introductionmentioning

confidence: 99%

Hybrid organic–inorganic compounds based on the Lindqvist polyoxomolybdate and dioxomolybdenum(vi) complexes

et al. 2011

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Organic-inorganic hybrids, based on the Lindqvist-type polyoxometalate (POM) and dioxomolybdenum(VI) complexes, have been synthesized by hydrolysis of [MoO 2 (acac) 2 ] (acac ¼ acetylacetonate) in the presence of aroylhydrazone ligands in weak donor solvents. This provides an efficient route to materials that contain open coordination sites or sites occupied by labile ligands. Removal upon grinding or heating of the labile acetonitrile and acetone molecules on the dioxomolybdenum centres and the reaction in the solid-state represent a way for designing structures with the Lindqvist Mo 6 O 19 2À anion coordinated to the metal centres of two complex cations. The compounds were characterised by the single crystal and powder X-ray diffraction methods, elemental analysis, IR spectroscopy, TG and DSC analyses.

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The crystallisation of polyoxo-molybdate and -tungstate anions with phenylated phosphonium and arsonium cations, in relation to the crystal packing and species in solution

Cited by 22 publications

References 30 publications

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

Intermolecular Embraces and Intermolecular Energies

Hybrid organic–inorganic compounds based on the Lindqvist polyoxomolybdate and dioxomolybdenum(vi) complexes

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