Spectroscopic and magnetic properties of two ferromagnetically coupled nickel(<scp>II</scp>) dimers [{Ni(terpy)(NCX)<sub>2</sub>}<sub>2</sub>](terpy = 2,2′ :6′,2″-terpyridine, X = S or Se). Crystal structure of the thiocyanate

Rojo, Teófilo; Cortés, Roberto; Lezama, Luís; Arriortua, Marı́a I.; Urtiaga, M. Karmele; Villeneuve, G.

doi:10.1039/dt9910001779

Cited by 60 publications

(22 citation statements)

References 21 publications

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“…The magnetic exchange constant for 1‐dimer can be compared with those reported for other Ni(NCS) 2 Ni dimers, recalculating all values to the J definition used within this report. In this case for [Ni(terpyridine)(NCS) 2 ] 2 a value of J = 14.0 K is obtained, while for [Ni 2 (en) 4 (SCN) 2 ]I 2 the exchange constant amounts to J = 14.4 K …”

Section: Resultsmentioning

confidence: 85%

Structural Diversity in Ni Chain Coordination Polymers: Synthesis, Structures, Isomerism and Magnetism

et al. 2018

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Reaction of Ni(NCS)2 with different co‐ligands based on pyridine derivatives substituted in 4‐position leads to the formation of 1D coordination polymers with the composition [Ni(NCS)2(co‐ligand)2]n, in which the metal cations are coordinated octahedrally by two S‐ and two N‐bonding thiocyanate anions as well as two neutral co‐ligands and are linked into chains by µ‐1,3‐bridging thiocyanate anions. Dependent on the nature of the co‐ligand, novel isomers with linear and corrugated chains are observed, in which the Ni cations are trans‐ or cis‐cis‐trans coordinated. This also includes a dimer and two isomeric chain compounds with 4‐chloropyridine as ligand, of which one is metastable at room‐temperature. For all these compounds, together with several additional Ni(NCS)2 chain compounds, the values of the intrachain exchange interaction J are extracted based on magnetic measurements. The values of J for 13 different Ni(NCS)2 compounds are compared with the structural results to investigate if there are some simple relations between the magnetic exchange, the metal coordination and the chain geometry. The low temperature magnetic properties of the Ni(NCS)2 dimer and the chain compounds are also discussed based on magnetic and specific heat measurements.

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Section: Resultsmentioning

confidence: 85%

Structural Diversity in Ni Chain Coordination Polymers: Synthesis, Structures, Isomerism and Magnetism

et al. 2018

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“…Unlike cyanate, the thiocyanate ion has often been reported as a suitable bridging ligand in coordination polymers. [34,35] The same is true of the homologous selenocyanate, although reports are rather rare. [35,36] In the solid state, the com-…”

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confidence: 66%

Pillars, Layers, Pores and Networks from Nickeltripyrrins: A Porphyrin Fragment as a Versatile Building Block for the Construction of Supramolecular Assemblies

Bröring

Prikhodovski

Brandt

et al. 2006

Chemistry A European J

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Sterically hindered nickel- tripyrrins [Ni(trpy)X] with different di-, tri- and tetradentate anions X have been prepared with the aim of finding coordination polymers formed by self-association. The syntheses were performed by simple ligand-exchange reactions and proceeded successfully with the pseudohalides CN(-), OCN(-), SCN(-), SeCN(-), N(CN)(2) (-) (dicyanoamido, dca) and C(CN)(3) (-) (tricyanomethanido, tcm), the cyanidometallates [Ag(CN)(2)](-) and [Ni(CN)(4)](2-) and the salicylate anion (sal(-)). X-ray crystallographic analyses revealed that the complexes with cyanido and isocyanato ligands, as well as the compound with a salicylato ligand, are prototypes for structurally distinct monomeric species in the solid state, whereas one-dimensional coordination polymers or supramolecular three-dimensional networks are formed from all other combinations. The polymeric compounds display a variety of individual pillar and network architectures with functionalised pores and clefts and with the Ni(trpy) fragments in different relative orientations. Hydrogen bonding and pi stacking were found to be additional structure-directing effects, which increased the structural complexity of the system. The Ni(trpy) subunit has thus been proven to be a versatile building block for the construction of supramolecular assemblies and metal organic frameworks (MOFs) from pentacoordinate Ni(II) ions.

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“…In combination with the low solubility of these species this finding points to the presence of bridging pseudohalide ligands for 7 and 8 and thus of coordination polymers in the solid state. The thiocyanate ion has frequently been reported as a bridging ligand in coordination polymers, [14,15] as has been for the homologous selenocyanate, although reports about the use of this nonconventional pseudohalide are rather rare. [15,16] In the IR spectra of the azido complex TrpyCdN 3 -(MeOH) (9) two equally intense bands are found in the region for the N 3 vibrations at 2090 and 2067 cm -1 .…”

Section: Resultsmentioning

confidence: 99%

Tripyrrinatocadmium Complexes: Enforcing Supramolecular Aggregation by a Large Ion

et al. 2007

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A newly developed method for the preparation of free base tripyrrin ligands HTrpy by cyanide‐promoted demetalation of nickel chelates TrpyNiNCO was used in order to explore the chemistry of cadmium tripyrrins TrpyCdX with a variety of anionic co‐ligands X. The introduction of the large CdII ion into the tripyrrin N3 coordination site was accomplished by the use of cadmium acetate as the metal precursor. Ligand exchange experiments using sodium salts of different anions disclose a marked tendency for pentacoordination, which is achieved either by the formation of chelates or of 1D coordination polymers that form as a consequence of the size of the central metal. The attempted introduction of chlorido, iodido, or cyanato ligands thus leads mainly to decomposed material, while the use of 1,1,1‐trifluoracetylacetonate, salicylate, and acetate ligands results in stable, pentacoordinate and monomeric complexes with the external ligand bound as a four‐ or six‐membered O,O‐chelate ring. With the pseudohalogenido ligands thiocyanate, selenocyanate, and azide as well as with the weakly coordinating trifluoroacetate 1D coordination polymers with a variety of chain structures were obtained and investigated by X‐ray diffraction studies. Interestingly TrpyCdN3 is present in the crystal as a coordinatively and hydrogen‐bonded methanol adduct with a dimeric repeating subunit. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Spectroscopic and magnetic properties of two ferromagnetically coupled nickel(II) dimers [{Ni(terpy)(NCX)₂}₂](terpy = 2,2′ :6′,2″-terpyridine, X = S or Se). Crystal structure of the thiocyanate

Cited by 60 publications

References 21 publications

Structural Diversity in Ni Chain Coordination Polymers: Synthesis, Structures, Isomerism and Magnetism

Structural Diversity in Ni Chain Coordination Polymers: Synthesis, Structures, Isomerism and Magnetism

Pillars, Layers, Pores and Networks from Nickeltripyrrins: A Porphyrin Fragment as a Versatile Building Block for the Construction of Supramolecular Assemblies

Tripyrrinatocadmium Complexes: Enforcing Supramolecular Aggregation by a Large Ion

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Spectroscopic and magnetic properties of two ferromagnetically coupled nickel(II) dimers [{Ni(terpy)(NCX)2}2](terpy = 2,2′ :6′,2″-terpyridine, X = S or Se). Crystal structure of the thiocyanate

Cited by 60 publications

References 21 publications

Structural Diversity in Ni Chain Coordination Polymers: Synthesis, Structures, Isomerism and Magnetism

Structural Diversity in Ni Chain Coordination Polymers: Synthesis, Structures, Isomerism and Magnetism

Pillars, Layers, Pores and Networks from Nickeltripyrrins: A Porphyrin Fragment as a Versatile Building Block for the Construction of Supramolecular Assemblies

Tripyrrinatocadmium Complexes: Enforcing Supramolecular Aggregation by a Large Ion

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Spectroscopic and magnetic properties of two ferromagnetically coupled nickel(II) dimers [{Ni(terpy)(NCX)₂}₂](terpy = 2,2′ :6′,2″-terpyridine, X = S or Se). Crystal structure of the thiocyanate