Structure and magnetic exchange in poly-bis(pyrazine)bis(methanesulfonato-<i>O</i>)-copper(II). One-dimensional exchange in a two-dimensional polymer

Haynes, John S.; Rettig, Steven J.; Sams, J. R.; Thompson, Robert C.; Trotter, James

doi:10.1139/v87-071

Cited by 68 publications

(27 citation statements)

References 10 publications

(13 reference statements)

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“…In summary, the spectroscopic studies have shown that all the compounds under consideration here are pseudo-octahedral complexes of high-spin iron(I1). The bis(pyrazine) complexes contain bridging pyrazine ligands and unidentate anions, with structures very probably similar to that of C U (~~Z )~( C H~S O~) (20) in which metal ions are bridged in a square array by neutral ligands and anions occupy transIaxial he sulfonate anions in the bis(pyridine) and the three mono(pyrazine) complexes are coordinated in a bidentate fashion yielding chromophores of the type FeN204. Although it is possible the anions are coordinated in a chelating fashion, this is considered unlikely given the strain that accompanies four membered chelate rings.…”

Section: Compound (K) (Mm S-i) (Mm S-i) (Mm S-i) (Mm S-i)mentioning

confidence: 97%

“…Such band splitting is not uncommon in pyrazine complexes and it has been suggested that it may arise from interactions between adjacent pyrazine rings or from different orientations of pyrazine rings giving rise to slightly different environments (2). It seems doubtful the splitting arises from significantly different structural environments for pyrazine rings as occurs in, for example, C U ( P Y Z )~( C H~S O~)~ (20). In this complex bridging pyrazine groups are of two types, one occupying equatorial positions and the other axial positions in the copper coordination sphere.…”

Section: Compound (K) (Mm S-i) (Mm S-i) (Mm S-i) (Mm S-i)mentioning

confidence: 99%

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Synthesis, spectroscopic and magnetic properties of some pyrazine-bridged iron(II) sulfonate complexes

Haynes¹,

Sams²,

Thompson³

1988

Can. J. Chem.

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Six new pyrazine-bridged complexes of iron(II) have been prepared and studied using magnetic susceptibility, differential scanning calorimetry, and vibrational, electronic, and Mössbauer spectroscopic methods. Fe(pyz)(CF3SO3)2 exhibits a susceptibility maximum at 4.4 K and analysis of the magnetic data according to a two-dimensional S = 2 system in the (isotropic) Heisenberg limit yields best-fit values of J = −0.26 cm−1 and g = 2.20. Variable temperature Mössbauer spectra between 4.2 and 1.6 K are also reported for this compound and show the onset of magnetic hyperfine splitting below ~3.8 K. Analysis of magnetic data for Fe(pyz)2(CH3SO3)2 and Fe(pyz)2(CF3SO3)2•CH3OH according to the two-dimensional Heisenberg model also indicates the presence of weak antiferromagnetic exchange in these complexes (J = −0.18 and −0.20 cm−1, respectively). No clear evidence for magnetic concentration was obtained from our studies on Fe(pyz)2(CIO4)2, Fe(pyz)(p-CH3C6H4SO3)2, and Fe(pyz)(p-CH3C6H4SO3)2•2CH3OH; any antiferromagnetic coupling in these complexes must be considerably weaker than in the other complexes studied.

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Section: Compound (K) (Mm S-i) (Mm S-i) (Mm S-i) (Mm S-i)mentioning

confidence: 97%

Section: Compound (K) (Mm S-i) (Mm S-i) (Mm S-i) (Mm S-i)mentioning

confidence: 99%

Synthesis, spectroscopic and magnetic properties of some pyrazine-bridged iron(II) sulfonate complexes

Haynes¹,

Sams²,

Thompson³

1988

Can. J. Chem.

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“…In contrast, the third one connects two Cu(3) ions from both axial and equatorial sites, as shown in Figure 1. As a result, the one-dimensional coordination framework composed of [-{Cu (1) 9 In this reaction, two starting [Cu(PF 6 ) 2 (py) 4 ] units dimerize with the removal of weakly coordinated PF 6 -anions and some py ligands and with an attack by MeOH molecules and MeO -anions. The dinuclear structure of 2 is shown in Figure 2.…”

mentioning

confidence: 99%

“…10 Each Cu atom shows a square-pyramidal coordination, with the basal plane formed by two N atoms of py (Cu-N = 2.000 (2) , which has a similar dinuclear structure except for the axial ligands. 8a,11 To compensate the charge balance, there are coordination-free PF 6 -anions in 2.…”

mentioning

confidence: 99%

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Synthesis and Crystal Structure of a One-dimensional Cu(II) Coordination Polymer Bridged by Inorganic CH3SO3− Anions Using Werner-type Cu(II) Complexes as Building Blocks

2012

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The reaction of [Cu(PF 6 ) 2 (py) 4 ] (py = pyridine) with [Cu(CH 3 SO 3 ) 2 (py) 4 ], both of which are Werner-type Cu(II) complexes, in a MeOH solution led to the formation of a onedimensional framework composed of [-{Cu (1) 6 (57 mg, 0.1 mmol) were dissolved in MeOH (10 mL) and excess diethyl ether was added to the MeOH solution. Then, the MeOH/diethyl ether solution was allowed to stand in a refrigerator. After a few hours, blue prismatic crystals of 1 and needle crystals, which have not yet been characterized, were obtained. ORTEP drawing of the one-dimensional chain of 1 (50% probability; symmetry operations: *-x + 1, -y + 1, -z + 1, **-x, -y, -z).The hydrogen atoms are omitted for clarity.The crystal structure of 1 was determined by a singlecrystal X-ray diffraction analysis at 173 K.7 Figure 1 shows the ORTEP view around the Cu(II) ions. In the crystal, there are three crystallographically independent Cu(II) ions bridged by inorganic CH 3 SO 3 -or organic MeO -anions. Cu(1) has a square-pyramidal environment with two py molecules and two MeO -anions in the equatorial plane and one CH 3 SO 3 -anion at an axial site. The Cu-O (CH 3 SO 3 -) bond distance of 2.409(3) Å is considerably longer than the equatorial Cu-N (py) and Cu-O (MeO -) distances (1.919(3)-2.011(3) Å), indicative of a Jahn-Teller effect. The remaining axial site is occupied by an oxygen atom of the CH 3 SO 3 -anion (Cu•••O distance = 2.829(3) Å) bridging between Cu(1) and Cu(2). Two MeO -anions bridge two Cu(1) ions to form the dinuclear core of {Cu 2 (MeO) 2 }, which has been seen in a large number of related Cu(II) complexes.8 Cu(2) forms an elongated octahedral center with four py molecules in the basal plane and two CH 3 SO 3 -anions (Cu(2)-O(2) = 2.506(3) and Cu(2)-O(4) = 2.377(3) Å) at the axial sites. This coordination environment is similar to that of the starting material, [Cu(CH 3 SO 3 ) 2 (py) 4 ]. Cu(3) also has an elongated octahedral environment with three py molecules and one CH 3 SO 3 -anion (Cu(3)-O(7) = 2.000(3) Å) in the equatorial plane and two CH 3 SO 3 -anions (Cu(3)-O(5) = 2.451(3) and Cu(3)-O(8)** = 2.371(3) Å, symmetry operation: *-x, -y, -z) at the axial sites. We found three crystallographically independent CH 3 SO 3 -anions. The first one bridges the Cu(1) and Cu(2) ions from the axial sites. The second one links the Cu(2) and Cu(3) ions from the axial sites. In contrast, the third one connects two Cu(3) ions from both axial and equatorial sites, as shown in Figure 1. As a result, the one-dimensional coordination framework composed of [-{Cu (1)

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Organisch-anorganische Hybridmaterialien: von „einfachen” Koordinationspolymeren zu Molybdänoxiden mit Organodiamin-Templaten

1999

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Eine Blaupause für das Design von Oxidmaterialien kann uns die Natur liefern, da sie bei Biomineralisationsprozessen und bei der Hydrothermalsynthese komplexer Mineralien anorganische Mikrostrukturen beeinflussen kann. Eine Anleihe bei dieser Fähigkeit führt zu einer ganz neuen Klasse von Materialien, bei denen organische Komponenten eine Rolle bei der Kontrolle über die anorganischen Mikrostrukturen spielen. Der Einsatz von Verbindungen aus der beständig wachsenden Klasse polymerer Komplexkationen ermöglicht die Herstellung von Molybdänoxiden mit neuartigen Substrukturen (siehe das im Bild gezeigte Beispiel).

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Structure and magnetic exchange in poly-bis(pyrazine)bis(methanesulfonato-O)-copper(II). One-dimensional exchange in a two-dimensional polymer

Cited by 68 publications

References 10 publications

Synthesis, spectroscopic and magnetic properties of some pyrazine-bridged iron(II) sulfonate complexes

Synthesis, spectroscopic and magnetic properties of some pyrazine-bridged iron(II) sulfonate complexes

Synthesis and Crystal Structure of a One-dimensional Cu(II) Coordination Polymer Bridged by Inorganic CH3SO3− Anions Using Werner-type Cu(II) Complexes as Building Blocks

Organisch-anorganische Hybridmaterialien: von „einfachen” Koordinationspolymeren zu Molybdänoxiden mit Organodiamin-Templaten

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