The Heptacyanotungstate(IV) Anion: A New 5 d Transition‐Metal Member of the Rare Heptacyanometallate Family of Anions

Birk, Francisco J.; Pinkowicz, Dawid; Dunbar, Kim R.

doi:10.1002/anie.201602949

Cited by 20 publications

(19 citation statements)

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“…[K(crypt‐222)] 3 [Mo IV (CN) 7 ]⋅3 CH 3 CN ( 2 ) has been crystallized from an acetonitrile solution containing the [Mo(CN) 8 ] 4− anion in the presence of [2.2.2]cryptand after white light irradiation (see details in the Supporting Information). The crystal structure of 2 has been solved and shows a [Mo IV (CN) 7 ] 3− (an analogue of [W IV (CN) 7 ] 3− ) anion (Tables S8, S9 and Figures , S13, and S14). Analysis of the [Mo IV (CN) 7 ] 3− coordination sphere revealed a pentagonal bipyramid with a CShM value of 0.26.…”

Section: Figurementioning

confidence: 99%

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Photoinduced Mo−CN Bond Breakage in Octacyanomolybdate Leading to Spin Triplet Trapping

Pillet

Graaf

et al. 2020

Angew Chem Int Ed

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The photoinduced properties of the octacoordinated complex K4MoIV(CN)8⋅2 H2O were studied by theoretical calculations, crystallography, and optical and magnetic measurements. The crystal structure recorded at 10 K after blue light irradiation reveals an heptacoordinated Mo(CN)7 species originating from the light‐induced cleavage of one Mo−CN bond, concomitant with the photoinduced formation of a paramagnetic signal. When this complex is heated to 70 K, it returns to its original diamagnetic ground state, demonstrating full reversibility. The photomagnetic properties show a partial conversion into a triplet state possessing significant magnetic anisotropy, which is in agreement with theoretical studies. Inspired by these results, we isolated the new compound [K(crypt‐222)]3[MoIV(CN)7]⋅3 CH3CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution.

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Section: Figurementioning

confidence: 99%

“…[K(crypt-222)] 3 [18] anion (Tables S8, S9 and Figures 4, S13, and S14). Analysis of the [Mo IV (CN) 7 ] 3À coordination sphere revealed ap entagonal bipyramid with aC ShM value of 0.26.…”

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confidence: 99%

Photoinduced Mo−CN Bond Breakage in Octacyanomolybdate Leading to Spin Triplet Trapping

Pillet

Graaf

et al. 2020

Angew Chem Int Ed

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“…22 The possible photoinduced metastable state [W IV (CN) 7 •CN] is supported by the recent report of the heptacyanotungstate(IV) complex anion, which is paramagnetic (S = 1). 23 The IR spectra recorded during the sample irradiation at 90 K present limited evidence for the aforementioned structural reorganization as the key for understanding the photomagnetism in 1 (Figure S17). Overall, the stunning photomagnetic behavior of 1 might be related to the improved flexibility of the CN-bridged framework after H 2 O removal, which enables the coordination sphere reorganization including the photodissociation of the nonbridging cyanide ligand.…”

Section: Journal Of the American Chemical Societymentioning

confidence: 99%

A Photomagnetic Sponge: High-Temperature Light-Induced Ferrimagnet Controlled by Water Sorption

et al. 2018

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tribute of molecule-based compounds called photomagnets and is inaccessible for conventional magnetic solids. The design and synthesis of such compounds, however, is a formidable challenge and only a few examples are known, all with rather low magnetic ordering temperatures well below the boiling point of liquid nitrogen. Herein, a cyanide-bridged coordination polymer {[Mn II (imidazole)]2[W IV (CN)8]}n exhibiting the highest light-induced magnetic ordering temperature ever observed and a magnetic hysteresis loop up to 90 K is reported. The photomagnetic effect results from the blue light excitation (450 nm) of the constituent octacyanotungstate(IV) moiety which then couples magnetically with manganese(II) resulting in light-induced ferrimagnetic ordering. The reported coordination framework shows also outstanding water sorption properties that are strongly correlated with the photomagnetic functionality. The photo-switching observed in the anhydrous state is completely quenched by the reversible capture of water with the fully hydrated phase becoming practically non-photomagnetic.

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“…Experimental and theoretical studies of seven-coordinated metal centers with pentagonal-bipyramidal (PBP) geometry (with a pseudo D 5h symmetry) show that such centers are promising as anisotropic spin carriers [9,11,[16][17][18][19][20][21][22][23][24]. As a result, new PBP complexes of 3d, 4d, 5d and 4f metals have been synthesized in recent years [25][26][27][28][29][30][31][32][33][34]. Among them, of special note are the seven-coordination PBP Dy complexes displaying high U eff and T B values, up to 1800 K and 20 K, respectively [3,19,[30][31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

A Series of Novel Pentagonal-Bipyramidal Erbium(III) Complexes with Acyclic Chelating N3O2 Schiff-Base Ligands: Synthesis, Structure, and Magnetism

et al. 2021

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A series of six seven-coordinate pentagonal-bipyramidal (PBP) erbium complexes, with acyclic pentadentate [N3O2] Schiff-base ligands, 2,6-diacetylpyridine bis-(4-methoxybenzoylhydrazone) [H2DAPMBH], or 2,6-diacethylpyridine bis(salicylhydrazone) [H4DAPS], and various apical ligands in different charge states were synthesized: [Er(DAPMBH)(C2H5OH)Cl] (1); [Er(DAPMBH)(H2O)Cl]·2C2H5OH (2); [Er(DAPMBH)(CH3OH)Cl] (3); [Er(DAPMBH)(CH3OH)(N3)] (4); [(Et3H)N]+[Er(H2DAPS)Cl2]− (5); and [(Et3H)N]+[Y0.95Er0.05(H2DAPS)Cl2]− (6). The physicochemical properties, crystal structures, and the DC and AC magnetic properties of 1–6 were studied. The AC magnetic measurements revealed that most of Compounds 1–6 are field-induced single-molecule magnets, with estimated magnetization energy barriers, Ueff ≈ 16–28 K. The experimental study of the magnetic properties was complemented by theoretical analysis based on ab initio and crystal field calculations. An experimental and theoretical study of the magnetism of 1–6 shows the subtle impact of the type and charge state of the axial ligands on the SMM properties of these complexes.

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The Heptacyanotungstate(IV) Anion: A New 5 d Transition‐Metal Member of the Rare Heptacyanometallate Family of Anions

Cited by 20 publications

References 28 publications

Photoinduced Mo−CN Bond Breakage in Octacyanomolybdate Leading to Spin Triplet Trapping

Photoinduced Mo−CN Bond Breakage in Octacyanomolybdate Leading to Spin Triplet Trapping

A Photomagnetic Sponge: High-Temperature Light-Induced Ferrimagnet Controlled by Water Sorption

A Series of Novel Pentagonal-Bipyramidal Erbium(III) Complexes with Acyclic Chelating N3O2 Schiff-Base Ligands: Synthesis, Structure, and Magnetism

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