Ionic Crystal Containing Protons (H<sup>+</sup>) as Counter Cations: Preparation and Crystal Structure of a Salt of 4,4′-Bipiperidine-1,1′-diium and Hexacyanidoferrate(II)

Tanaka, Rikako; Okazawa, Atsushi; Kojima, Naoya; Matsushita, Nobuyuki

doi:10.1246/cl.180157

Cited by 6 publications

(4 citation statements)

References 25 publications

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“…These changes could be easily observed by the naked eye. Trying to obtain SCXRD-quality crystals, we used stable hexacyanoferric(II) acid (H 4 [Fe(CN) 6 ]) as a source of HCF since numerous crystalline structures of organic hexacyanoferrates, including the pyridinium-type cations, have been prepared and described [20][21][22][23][24]. Many such complexes contain protonated cyanoferrate(II) platforms, and therefore, regardless of the charge of the organic cation, they have different molecular formulas, determined by the different charge of the cyanoferrate(II).…”

Section: Inter-ionic Charge-transfer Hexacynoferrate(ii) Supramolecul...mentioning

confidence: 99%

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Supramolecular Solid Complexes between Bis-pyridinium-4-oxime and Distinctive Cyanoiron Platforms

Picek,

Matković-Čalogović,

Dražić

et al. 2024

Molecules

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The structural features and optical properties of supramolecular cyanoiron salts containing bis-pyridinium-4-oxime Toxogonin® (TOXO) as an electron acceptor are presented. The properties of the new TOXO-based cyanoiron materials were probed by employing two cyanoiron platforms: hexacyanoferrate(II), [Fe(CN)6]4– (HCF); and nitroprusside, [Fe(CN)5(NO)]2– (NP). Two water-insoluble inter-ionic donor–acceptor phases were characterized: the as-prepared microcrystalline reddish-brown (TOXO)2[Fe(CN)6]·8H2O (1a) with a medium-responsive, hydrochromic character; and the dark violet crystalline (TOXO)2[Fe(CN)6]·3.5H2O (1cr). Complex 1a, upon external stimulation, transforms to the violet anhydrous phase (TOXO)2[Fe(CN)6] (1b), which upon water uptake transforms back to 1a. Using the NP platform resulted in the water-insoluble crystalline salt TOXO[Fe(CN)5(NO)]·2H2O (2). The structures of 1cr and 2, solved by single-crystal X-ray diffraction, along with a comparative spectroscopic (UV–vis–NIR diffuse reflectance, IR, solid-state MAS-NMR, Mössbauer), thermal, powder X-ray diffraction, and microscopic analysis (SEM, TEM) of the isolated materials, provided insight for the supramolecular binding, electron-accepting, and H-bonding capabilities of TOXO in the self-assembly of these functionalized materials.

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Section: Inter-ionic Charge-transfer Hexacynoferrate(ii) Supramolecul...mentioning

confidence: 99%

“…Once precipitated from aqueous solution, the solids could not be re-dissolved in water or in common polar organic solvents such as MeOH, EtOH, acetone, and DMSO. The H 4 [Fe(CN) 6 ] was synthetized following the procedure described in [22].…”

Section: Isolation Of Supramolecular Complexesmentioning

confidence: 99%

Supramolecular Solid Complexes between Bis-pyridinium-4-oxime and Distinctive Cyanoiron Platforms

Picek,

Matković-Čalogović,

Dražić

et al. 2024

Molecules

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“…[1][2][3][4][5][6] For ionic solids, the arrangement of ionic molecular species is commonly governed by Coulombic forces to minimize electrostatic energy, forming an alternate arrangement of cationic and anionic species. [7][8][9][10][11][12] In some supramolecular coordination systems, it has been recognized that the introduction of noncovalent interactions, such as hydrogen-bonding and π interactions, leads to special arrangements of ionic species in the solid state. [13][14][15][16][17][18][19] However, reports on ionic solids that show a nonalternate arrangement of cationic and anionic species against Coulombic forces are still limited in number.…”

Section: Introductionmentioning

confidence: 99%

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

Pratikha

Inoue

Arai

et al. 2020

J Chinese Chemical Soc

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The reaction of Na[Co III (D-ebp)] (D-H 4 ebp = N,N 0-ethylenebis[D-penicillamine]) with [(Au I Cl) 2 (dppe)] (dppe = 1,2-bis[diphenylphosphino]ethane) gave a cationic Au I 4 Co III 2 hexanuclear complex, [Co III 2 (L Au4)] 2+ ([1] 2+), where [L Au4 ] 4− is a cyclic tetragold(I) metalloligand with a 32-membered ring, [Au I 4 (dppe) 2 (D-ebp) 2 ] 4−. Complex [1] 2+ crystallized with NO 3 − to produce a charge-separation (CS)-type ionic solid of [1](NO 3) 2. In [1](NO 3) 2 , the complex cations are assembled to form cationic supramolecular hexamers of {[1] 2+ } 6 , which are closely packed in a face-centered cubic (fcc) lattice structure. The nitrate anions of [1](NO 3) 2 were accommodated in hydrophilic and hydrophobic tetrahedral interstices of the fcc structure to form tetrameric and hexameric nitrate clusters of {NO 3 − } 4 and {NO 3 − } 6 , respectively. An analogous CS-type ionic solid formulated as [Ni II Co III (L Au4)](NO 3) ([2](NO 3)) was obtained when a 1:1 mixture of Na[Co III (D-ebp)] and [Ni II (D-H 2 ebp)] was reacted with [(Au I Cl) 2 (dppe)], accompanied by the conversion of the diamagnetic, squareplanar [Ni II (D-H 2 ebp)] to the paramagnetic, octahedral [Ni II (D-ebp)] 2−. While the overall fcc structure in [2](NO 3) was similar to that of [1](NO 3) 2 , none of the nitrate anions were accommodated in any hydrophobic tetrahedral interstice, reflecting the difference in the complex charges between [1] 2+ and [2] + .

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“…Because of their higher nucleophilicity in comparison with purely organic molecules, inorganic coordination compounds are increasingly used as halogen bond acceptors. − Particularly useful are cyanometalates [M(CN) x ] z − due to their highly variable topologies and their strongly coordinating properties . While a few examples of cyanometalates as halogen bond acceptors have been reported, − their ability to form strong hydrogen bonds (and also network structures) has to be taken into account. − Consequently, the crystal engineering of networks involving both hydrogen and halogen bonding is especially challenging . Furthermore, their tendency for significant deviations from linear halogen bonds (CN···I ≠ 180°) reduces the structural predictability of such interactions .…”

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confidence: 99%

Cubic Three-Dimensional Networks of the Cyanometalate [Fe(CN)₆]³^– with the Ditopic Halogen Bond Donor Diiodoacetylene C₂I₂

Sellin

Rupf

Malischewski

2021

Crystal Growth & Design

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Halogen-bonded networks have been prepared by cocrystallization of the linear ditopic halogen bond donor diiodoacetylene C2I2 and lipophilic phosphonium salts of the octahedral hexatopic halogen bond acceptor hexacyanoferrate(III) [Fe(CN)6]3–. The crystal structure of [PPh3Me]3[Fe(CN)6]·3C2I2·7.5MeCN displays a two-fold interpenetrated, three-dimensional cubic halogen-bonded network, in which the CN···I angles are almost linear (170.4(4) and 167.6(4)°). In the case of [PPh4]3[Fe(CN)6]·4C2I2·6CH3CN, a two-dimensional ribbon structure with mono- and bifurcated acceptor sites is observed, while [PNP]3[Fe(CN)6]·4C2I2·4CH2Cl2 displays a three-dimensional halogen-bonded network structure. In the latter two structures, CN···I angles are in the range of 99.2(6)–161.8(6)° and 118.9(2)–143.1(2)°, respectively. This finding illustrates the high structural flexibility of C2I2 coordination to cyanide ligands, which is supposed to be a consequence of packing effects.

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Ionic Crystal Containing Protons (H⁺) as Counter Cations: Preparation and Crystal Structure of a Salt of 4,4′-Bipiperidine-1,1′-diium and Hexacyanidoferrate(II)

Cited by 6 publications

References 25 publications

Supramolecular Solid Complexes between Bis-pyridinium-4-oxime and Distinctive Cyanoiron Platforms

Supramolecular Solid Complexes between Bis-pyridinium-4-oxime and Distinctive Cyanoiron Platforms

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

Cubic Three-Dimensional Networks of the Cyanometalate [Fe(CN)₆]³^– with the Ditopic Halogen Bond Donor Diiodoacetylene C₂I₂

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Ionic Crystal Containing Protons (H+) as Counter Cations: Preparation and Crystal Structure of a Salt of 4,4′-Bipiperidine-1,1′-diium and Hexacyanidoferrate(II)

Cited by 6 publications

References 25 publications

Supramolecular Solid Complexes between Bis-pyridinium-4-oxime and Distinctive Cyanoiron Platforms

Supramolecular Solid Complexes between Bis-pyridinium-4-oxime and Distinctive Cyanoiron Platforms

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

Cubic Three-Dimensional Networks of the Cyanometalate [Fe(CN)6]3– with the Ditopic Halogen Bond Donor Diiodoacetylene C2I2

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Product

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Ionic Crystal Containing Protons (H⁺) as Counter Cations: Preparation and Crystal Structure of a Salt of 4,4′-Bipiperidine-1,1′-diium and Hexacyanidoferrate(II)

Cubic Three-Dimensional Networks of the Cyanometalate [Fe(CN)₆]³^– with the Ditopic Halogen Bond Donor Diiodoacetylene C₂I₂