A toolbox of building blocks, linkers and crystallisation methods used to generate single-chain magnets

Dhers, Sébastien; Feltham, Humphrey L. C.; Brooker, Sally

doi:10.1016/j.ccr.2015.03.012

Cited by 152 publications

(94 citation statements)

References 152 publications

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“…The synthesis of new coordination compounds including polymers, metal organic frameworks, or inorganic‐organic hybrid compounds is still an important field in coordination chemistry because many of them have some potential for future applications . In most cases coordination compounds are synthesized from solution, but there are also some examples, in which such compounds were prepared by solid‐state routes, like, e.g.…”

Section: Introductionmentioning

confidence: 99%

Zn(NCS)₂‐3‐cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

Jochim

Jeß

Näther

2018

Zeitschrift anorg allge chemie

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The reaction of different stoichiometric amounts of Zn(NCS) 2 with 3-cyanopyridine in different solvents leads to the formation of several new coordination compounds, which were structurally characterized and investigated for their thermal behavior. In Zn(NCS) 2 (3-cyanopyridine) 4 (1) and Zn(NCS) 2 (3-cyanopyridine) 2 (H 2 O) 2 · (3-cyanopyridine) 2 (2) the zinc cations are octahedrally coordinated by two terminally N-bonded thiocyanate anions and four 3-cyanopyridine (1) or two 3-cyanopyridine and two water molecules (2) within slightly distorted octahedra. Zn(NCS) 2 (3-cyanopyridine) 2 (3) and Zn(NCS) 2 (3cyanopyridine) 2 ·(H 2 O) 0.5 (3-H 2 O) also form discrete complexes but 212 with tetrahedrally coordinated Zn cations. Upon heating compound 1 decomposes without the formation of any intermediate compound. In contrast, compound 2 loses the water molecules in the first step and transforms into compound 1. Surprisingly, upon further heating a second TG step is observed, in which compound 3 is formed as an intermediate, which is not observed if compound 1 is heated directly. The tetrahedral complex 3 melts leading to the formation of an amorphous phase. If the hemihydrate 3-H 2 O is heated, it transforms into 3 via melting and crystallization but there are hints that a metastable phase might form as intermediate on water removal.

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Section: Introductionmentioning

confidence: 99%

Zn(NCS)₂‐3‐cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

Jochim

Jeß

Näther

2018

Zeitschrift anorg allge chemie

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“…Purely organic molecular materials that show electric conductivity and non-trivial magnetic properties [1][2][3][4] are at the forefront of molecular materials science due to the tremendous flexibility and tunability of organic molecules. Moreover, the potential synergy and interplay between the properties of redox-active organic molecules and metal complexes open new routes to redox-active multistable systems [5,6], single molecule magnets (SMMs) and single chain magnets (SCMs) [7][8][9], and switchable magnetic conductors [10,11]. Achievement of such advanced properties requires, however, an expansion of the library of easily accessible and electroactive molecules with relatively stable radical forms.…”

Section: Introductionmentioning

confidence: 99%

Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties

2019

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Phenanthroline dioxothiadiazoles are redox active molecules that form stable radical anions suitable for the construction of supramolecular magnetic materials. Herein, the preparation, structures and magnetic properties of bis(triphenylphosphine)iminium (PPN) salts of [1,2,5]thiadiazole[3,4-f][1,10]phenanthroline 1,1-dioxide (L), [1,2,5]thiadiazole[3,4-f][4,7]phenanthroline 1,1-dioxide (4,7-L), 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL), and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL) are reported. The preparation of new bromo derivatives of the L: 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL) and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL)—suitable starting materials for further derivatization—are described starting from a commercially available and cheap 1,10-phenanthroline. All PPN salts show antiferromagnetic interactions between the pairs of radical anions, which in the case of PPN(diBrL) are very strong (−116 cm−1; using Ĥ = −2JSS type of exchange coupling Hamiltonian) due to a different crystal packing of the anion radicals as compared to PPN(L), PPN(4,7-L), and PPN(BrL).

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“…The synthesis of new magnetic coordination compounds is still an important topic in modern coordination chemistry and an extremely large number of compounds showing a variety of magnetic properties has been reported . In this regard one‐dimensional coordination polymers, for which the magnetic properties largely depend on the strength of the exchange along the chains are of special interest . This interaction is predominantly determined by the bridging ligand that mediates the magnetic exchange and therefore, replacement of one ligand by a different one is one possibility to influence the magnetic properties of such compounds in a desired way.…”

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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A toolbox of building blocks, linkers and crystallisation methods used to generate single-chain magnets

Cited by 152 publications

References 152 publications

Zn(NCS)₂‐3‐cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

Zn(NCS)₂‐3‐cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties

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

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A toolbox of building blocks, linkers and crystallisation methods used to generate single-chain magnets

Cited by 152 publications

References 152 publications

Zn(NCS)2‐3‐cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

Zn(NCS)2‐3‐cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties

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

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Product

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Zn(NCS)₂‐3‐cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

Zn(NCS)₂‐3‐cyanopyridine Coordination Compounds: Synthesis, Crystal Structures, and Thermal Properties

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