Polymeric [(Me3Sn)3Rh(SCN)6]: A Novel “Super‐Prussian‐Blue” Derivative Containing the Nonlinear ‐SCN‐Sn‐NCS‐ Spacer

Siebel, Eric; Fischer, R.

doi:10.1002/chem.19970031213

Cited by 31 publications

(8 citation statements)

References 26 publications

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“…48 Not only transition metals, but also main group metals with chelate ligands, such as the (SnMe 3 ) + cation, are prospective linkers for binding the cyanometallate complexes and can be used in the synthesis of so called super Prussian blue structures based on the cyanometallates [M(CN) 6 ] nÀ . 68,69 We studied the interaction of the anionic cluster complexes [Re 6 Se 8 (CN) 6 ] 4À and SnMe 3 Cl, varying the acidity of the medium, 53 and showed that the type of polymer formed is mainly determined by the synthesis conditions, i.e., the ''charge'' stoichiometry, the temperature, and pH of the medium. 70 Unlike with transition metals, the Sn atom has, as a rule, coordination number 5 (triangular bipyramid), with the methyl groups in the equatorial plane and the axial trans-positions available to the other ligands L for coordination.…”

Section: And Their Variation Depending On Metal Cation Complexesmentioning

confidence: 99%

Novel compounds based on [Re6Q8(L)6]4− (Q = S, Se, Te; L = CN, OH) and their applications

2009

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Se, Te) clusters can serve as promising ''building blocks'' for the creation of new porous framworks, nanoparticles and mesoporous materials. Since [Re 6 Q 8 L 6 ] 4À clusters have multianchoring sites for transition metals, metal-organic complexes, polymers, and multidentated metal complexes, they could be assembled to form various inorganic or organic-inorganic hybrid solids with new various spatial and chemical functions. Because of the controllable architectures and multianchoring sites of clusters together with their photoluminescence, rhenium cluster complexes are promising potential candidates as catalysts, chemical color sensors, magnetic materials, gas storage materials, optoelectronic, diagnostic agents, and gene/drug carriers. A new type of mesoscale material comprising [Re 6 Q 8 (CN) 6 ] 4À and various divalent transition metals in the presence of a liquid crystal template are obtained in 3D cubic, 2D hexagonal, and lamellar phases. The hexahydroxo complexes [Re 6 Q 8 (OH) 6 ] 4À (Q ¼ S, Se) with high reactivities and a unique rhenium sulfido-cyanide compound, K 8 [Re 12 CS 17 (CN) 6 ] with a C-centered {Re 12 } cluster unit were discovered and still many more new rhenium metal cluster complexes at various reaction conditions remain to be explored.

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Section: And Their Variation Depending On Metal Cation Complexesmentioning

confidence: 99%

Novel compounds based on [Re6Q8(L)6]4− (Q = S, Se, Te; L = CN, OH) and their applications

2009

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“…These MOFs with microporosity might be good candidates for storage of small molecules like hydrogen, and further investigation will be performed. As far as we known, the numerous MOFs of α-Po topology are 2-fold or 3-fold interpenetrated frameworks. ,− Complexes 1 − 3 are the scarce examples of non-interpenetrated structures of the topology. The topologies of these complexes are similar to Zn 2 (trz) 2 (ox) which are constructed from comparable (4,4) layers that are further connected to 3-D networks by bridging ligands …”

Section: Resultsmentioning

confidence: 99%

Structural, Luminescent, and Magnetic Properties of Three Novel Three-Dimensional Metal-Organic Frameworks Based on Hexadentate N,N′-bis(4-picolinoyl)hydrazine

Fang

et al. 2009

Inorg. Chem.

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Three novel microporous three-dimensional (3-D) metal-organic framework materials [ML](n) [M = Ni, Co, Cd; L = N,N'-bis(4-picolinoyl)hydrazine] were obtained from hydrothermal reactions. The organic ligand L was formed through the in situ ring-opening hydrolysis reaction of 2,5-bis(4-pyridyl)-1,3,4-oxadiazole with the assistance of metal ions. Single-crystal X-ray diffraction studies reveal that complexes 1-3 adopt 6-connected 3-D networks of distorted alpha-Po topology, which are built from non-interpenetrated (4,4) grids cross-linked by zigzag chains. These isomorphic complexes are all of high thermal stability, but some other physical properties are quite different because of their different metal centers. Antiferromagnetic exchange was observed between Ni(II) centers of complex 1, while ferromagnetic for Co(II) centers of complex 2. Complex 3 exhibits strong fluorescence emission.

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“…The stock solution of K 3 [Rh III (SCN) 6 ] was prepared according to the literature procedure with some modifications. 31 An aqueous solution of potassium thiocyanate (1.0 M, 30 mL) was heated to 100 °C and magnetically stirred, followed by the slow addition of an aqueous solution of rhodium(III) chloride trihydrate (0.57 M, 10 mL) for 2 h. After the reaction solution was cooled to room temperature, distilled water (25 mL) was slowly added to the obtained slurry and then evaporated under reduced pressure. After this procedure was repeated two times, absolute ethanol was added to the residue to extract the crude products.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Selective Crystallization of Linkage Isomers, [Rh^III(NCS)(SCN)₅]^3– and [Rh^III(SCN)₆]^3–, to Investigate Structural Trans Influence and Thermal Stability

Mukai,

Hagiwara,

Tanaka

et al. 2023

Inorg. Chem.

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Linkage isomers of homoleptic complexes, [Rh III (SCN) 6 ] 3− and [Rh III (NCS)(SCN) 5 ] 3− , formed in aqueous solution were successfully separated by employing methyltriphenylphosphonium (MePPh 3 + ) and 1-ethylquinolinium (EtQu + ) ions as countercations, respectively. The single-crystal X-ray analysis of (MePPh 3 ) 3 [Rh III (SCN) 6 ] (1) indicated that all of the SCN − ligands coordinate to the Rh III ion by S atoms with an octahedral symmetry, where the average bond length of Rh−S is 2.374(7) Å. On the other hand, the Rh III ion of (EtQu 2) is coordinated by five S atoms and one N atom of the SCN − ligands with a C 4v symmetry. Structural trans influence was observed in the shorter bond length of Rh−S at the trans position of Rh−N. The Rh−S bond length is 2.3398(13) Å significantly shorter than those of 1 by ca. 0.04 Å, although DFT calculations based on the crystal structures indicated that the effective bond order of Rh−N is higher than those of Rh−S. Thermal stability examination by thermogravimetric and differential thermal analyses (TG/DTA) and IR spectroscopy indicated that the linkage isomerization of [Rh III (SCN) 6 ] 3− to [Rh III (NCS)(SCN) 5 ] 3− proceeded after melting around 174 °C. These results clearly indicate that [Rh III (NCS)(SCN) 5 ] 3− is thermodynamically more stable than [Rh III (SCN) 6 ] 3− in solid states, although further linkage isomerization hardly occurs.

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Polymeric [(Me₃Sn)₃Rh(SCN)₆]: A Novel “Super‐Prussian‐Blue” Derivative Containing the Nonlinear ‐SCN‐Sn‐NCS‐ Spacer

Abstract: Abstract:The new coordination polymer [(Me,Sn'v)

Cited by 31 publications

References 26 publications

Novel compounds based on [Re6Q8(L)6]4− (Q = S, Se, Te; L = CN, OH) and their applications

Novel compounds based on [Re6Q8(L)6]4− (Q = S, Se, Te; L = CN, OH) and their applications

Structural, Luminescent, and Magnetic Properties of Three Novel Three-Dimensional Metal-Organic Frameworks Based on Hexadentate N,N′-bis(4-picolinoyl)hydrazine

Selective Crystallization of Linkage Isomers, [Rh^III(NCS)(SCN)₅]^3– and [Rh^III(SCN)₆]^3–, to Investigate Structural Trans Influence and Thermal Stability

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Polymeric [(Me3Sn)3Rh(SCN)6]: A Novel “Super‐Prussian‐Blue” Derivative Containing the Nonlinear ‐SCN‐Sn‐NCS‐ Spacer

Abstract: Abstract:The new coordination polymer [(Me,Sn'v)

Cited by 31 publications

References 26 publications

Novel compounds based on [Re6Q8(L)6]4− (Q = S, Se, Te; L = CN, OH) and their applications

Novel compounds based on [Re6Q8(L)6]4− (Q = S, Se, Te; L = CN, OH) and their applications

Structural, Luminescent, and Magnetic Properties of Three Novel Three-Dimensional Metal-Organic Frameworks Based on Hexadentate N,N′-bis(4-picolinoyl)hydrazine

Selective Crystallization of Linkage Isomers, [RhIII(NCS)(SCN)5]3– and [RhIII(SCN)6]3–, to Investigate Structural Trans Influence and Thermal Stability

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Polymeric [(Me₃Sn)₃Rh(SCN)₆]: A Novel “Super‐Prussian‐Blue” Derivative Containing the Nonlinear ‐SCN‐Sn‐NCS‐ Spacer

Selective Crystallization of Linkage Isomers, [Rh^III(NCS)(SCN)₅]^3– and [Rh^III(SCN)₆]^3–, to Investigate Structural Trans Influence and Thermal Stability