Synthesis, Structure, and Properties of Coordination Polymers with Layered Transition‐Metal Thiocyanato Networks

Werner, Julia; Tomkowicz, Z.; Reinert, Thorben; Näther, Christian

doi:10.1002/ejic.201500176

Cited by 36 publications

(31 citation statements)

References 52 publications

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“…Only one topology is known for cobalt compounds of this composition, in which every two cobalt cations are connected by a pair of -1,3-bridging thiocyanate anions, forming dimers, which are connected to four adjacent dimers by single -1,3-bridging thiocyanate anions (Wö hlert & Nä ther, 2013;Suckert et al, 2016Suckert et al, , 2017Werner et al, 2015b). Nevertheless, with other metal cations different layer topologies are known in which, for example, trimers are formed instead of dimers, which are connected by single -1,3thiocyanate bridges (Kozísková et al, 1990;Kabešová et al, 1990) or in which each metal cation is directly connected to four neighboring metal cations by single -1,3-thiocyanate bridges (McElearney et al, 1979;Werner et al, 2015c;Ðaković et al, 2010). Although it is not clear by which parameters the formation of either chains or layers is promoted, a third isomer of composition Co(NCS) 2 (L) 2 exists in which the thiocyanate anions are N-terminally coordinated, forming discrete tetrahedral complexes (Prananto et al, 2017;Neumann et al, 2018c;Hannachi et al, 2019).…”

Section: Chemical Contextmentioning

confidence: 99%

Crystal structure of bis(N,N′-dimethylthiourea-κS)bis(thiocyanato-κN)cobalt(II)

et al. 2020

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During systematic investigations on the synthesis of coordination polymers with Co(NCS)2 involving different thiourea derivatives as coligands, crystals of the title compound Co(NCS)2(N,N′-dimethylthiourea)2, or [Co(C3H8N2S)2(NCS)2], were obtained. These crystals were non-merohedric twins and therefore, a twin refinement using data in HKLF-5 format was performed. In the crystal structure of this compound, the CoII cations are coordinated by two N-terminally bonded thiocyanate anions as well as two S-bonding N,N′-dimethylthiourea molecules, forming two crystallographically independent discrete complexes each with a strongly distorted tetrahedral geometry. An intricate network of intermolecular N—H...S and C—H...S hydrogen bonds can be found between the complexes. The thermogravimetric curve of the title compound shows two discrete steps in which all coligand molecules have been emitted, which is also accompanied by partial decomposition of the cobalt thiocyanate. If the measurement is stopped after the first mass loss, only broad reflections of CoS can be found in the XRPD pattern of the residue, which proves that this compound decomposes completely upon heating. However, at lower temperatures an endothermic signal can be found in the DTA and DSC curve, which corresponds to melting, as proven by thermomicroscopy.

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Section: Chemical Contextmentioning

confidence: 99%

Crystal structure of bis(N,N′-dimethylthiourea-κS)bis(thiocyanato-κN)cobalt(II)

et al. 2020

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“…If the precursors consist of discrete complexes with pyridine derivatives as co‐ligands, usually 1D compounds are obtained, in which the metal cations are octahedrally coordinated by two N‐donor co‐ligands as well as four μ‐1,3‐bridging anionic ligands and are linked by pairs of anionic ligands into chains, although examples of 2D networks are also known , . The 1D compounds with Co II are of special interest, because the magnetic exchange along the chain is ferromagnetic and several of these coordination polymers show single chain magnetism , , .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structures, and Properties of Ni(NCS)₂‐4‐methoxypyridine Coordination Compounds

Jochim

Ceglarska

Rams

et al. 2018

Zeitschrift anorg allge chemie

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Two polymorphs of Ni(NCS)2(4‐methoxypyridine)4 (1‐I, 1‐II) as well as compounds with the compositions Ni(NCS)2(4‐methoxypyridine)4(MeCN)1.33 (1‐MeCN), Ni(NCS)2(4‐methoxypyridine)2(MeCN)2 (2) and [Ni(NCS)2(4‐methoxypyridine)2]n (3) are reported. For 1‐II no single crystals were obtained, but this compound is isotypic to the Fe analog 1‐II‐Fe. The crystal structures of 1 and 2 show discrete octahedral NiII complexes, whereas in 3 the cations are connected by pairs of thiocyanate anions into chains. Solvent mediated conversion experiments reveal that 1‐I is thermodynamically stable at room temperature and differential scanning calorimetry shows no indication for a polymorphic transition. The thermal behavior of 1‐I, 1‐II, and 2 was investigated by simultaneous thermogravimetry and differential scanning calorimetry, which shows that they decompose in two discrete steps. In the first step compound 3 is formed as an intermediate, which decomposes on further heating into Ni(NCS)2. Time dependent XRPD investigations prove, that 2 transforms already at room temperature into 3. Upon heating 1‐MeCN transforms into 1‐I in the first TG step, which decomposes on further heating into 3. Investigation of the magnetic behavior of 3 shows dominating ferromagnetic exchange interactions along the chains with J = 5.9(1) K. Susceptibility measurements indicate antiferromagnetic ordering, which was confirmed by specific heat measurements, revealing that magnetic ordering occurs at 1.91(5) K.

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“…[1][2][3][4][5][6][7][8][9][10][11][12] In this context, compounds, in which the paramagnetic metal cations are linked by bridging ligands, are of special interest, because they can show cooperative magnetic phenomena. [13][14][15][16][17][18][19][20] On the other hand, also compounds based on diamagnetic Zn II and Cd II are of interest, because they can exhibit luminescence properties with a variety of ligands.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures, and Physical Properties of Thiocyanate Coordination Compounds with 3‐Hydroxymethylpyridine

Neumann

Cunha

Terraschke

et al. 2017

Zeitschrift anorg allge chemie

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Abstract. The reaction of Cd(NCS) 2 with 3-hydroxymethylpyridine (3-HMPy) leads to the formation of compounds with the composition Cd(NCS) 2 (3-HMPy) 4 (1-Cd),Cd(NCS) 2 (3-HMPy) 2 (2-Cd)(Cd(NCS) 2 ) 2 -(3-HMPy) 3 (3-Cd), and (Cd(NCS) 2 ) 3 (3-HMPy) 4 (4-Cd). Compound 1-Cd consists of discrete complexes and in 2-Cd the Cd cations are linked into chains by the anionic and the organic co-ligands. In 3-Cd as well as 4-Cd the Cd cations are connected into chains by the thiocyanate anions, which are further linked into layers by the 3-HMPy coligands. In contrast, with Zn only one compound with the composition Zn(NCS) 2 (3-HMPy) 2 ·H 2 O (1-Zn-H 2 O) was characterized by single-

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Synthesis, Structure, and Properties of Coordination Polymers with Layered Transition‐Metal Thiocyanato Networks

Abstract: Reaction of 4-tert-butylpyridine (tBP) with transition-metal thiocyanates leads to the formation of compounds of compo-

Cited by 36 publications

References 52 publications

Crystal structure of bis(N,N′-dimethylthiourea-κS)bis(thiocyanato-κN)cobalt(II)

Crystal structure of bis(N,N′-dimethylthiourea-κS)bis(thiocyanato-κN)cobalt(II)

Synthesis, Crystal Structures, and Properties of Ni(NCS)₂‐4‐methoxypyridine Coordination Compounds

Synthesis, Structures, and Physical Properties of Thiocyanate Coordination Compounds with 3‐Hydroxymethylpyridine

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Synthesis, Structure, and Properties of Coordination Polymers with Layered Transition‐Metal Thiocyanato Networks

Abstract: Reaction of 4-tert-butylpyridine (tBP) with transition-metal thiocyanates leads to the formation of compounds of compo-

Cited by 36 publications

References 52 publications

Crystal structure of bis(N,N′-dimethylthiourea-κS)bis(thiocyanato-κN)cobalt(II)

Crystal structure of bis(N,N′-dimethylthiourea-κS)bis(thiocyanato-κN)cobalt(II)

Synthesis, Crystal Structures, and Properties of Ni(NCS)2‐4‐methoxypyridine Coordination Compounds

Synthesis, Structures, and Physical Properties of Thiocyanate Coordination Compounds with 3‐Hydroxymethylpyridine

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Synthesis, Crystal Structures, and Properties of Ni(NCS)₂‐4‐methoxypyridine Coordination Compounds