Electron Paramagnetic Resonance of Dipyridyl-Coordinated Ag2+(4d9)

Halpern, T.; McKoskey, Susan M.; McMillan, J. A.

doi:10.1063/1.1673517

Cited by 25 publications

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“…Numerous two-dimensional (2D) antiferromagnets of Cu 2+ ions exist, but there is no proven 2D antiferromagnet of Ag 2+ ions. Lewis bases such as pyridine (py), 2,2′-bipyridine (2,2′-bipy), and 1,4,8,11-tetraazacyclotetradecane are known to stabilize Ag 2+ ions in the solid state. Ag(py) 4 (S 2 O 8 ) apparently consists of square planar Ag 2+ ions surrounded by the nitrogen atoms of four py ligands although it is unclear whether the S 2 O 8 2− anion is also coordinated .…”

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“…Lewis bases such as pyridine (py), 2,2′-bipyridine (2,2′-bipy), and 1,4,8,11-tetraazacyclotetradecane are known to stabilize Ag 2+ ions in the solid state. Ag(py) 4 (S 2 O 8 ) apparently consists of square planar Ag 2+ ions surrounded by the nitrogen atoms of four py ligands although it is unclear whether the S 2 O 8 2− anion is also coordinated . A promising candidate for a 2D antiferromagnet of Ag 2+ ions is Ag(pyz) 2 (S 2 O 8 ) (pyz = pyrazine) reported nearly four decades ago.…”

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Characterization of the Antiferromagnetism in Ag(pyz)₂(S₂O₈) (pyz = Pyrazine) with a Two-Dimensional Square Lattice of Ag²⁺ Ions

et al. 2009

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Characterization of the Antiferromagnetism in Ag(pyz)₂(S₂O₈) (pyz = Pyrazine) with a Two-Dimensional Square Lattice of Ag²⁺ Ions

et al. 2009

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“…Reference[18]. Reference[31]; Reference[32]; Reference [19]; ' Reference [14]; ' Reference [15]; ' Reference [3]; Reference [4]; ' Reference [33]; This work.…”

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Presence of Jahn-Teller distortions in a novel six-coordinate Ag(II) complex: temperature dependent EPR, optical and magnetic susceptibility measurements

Kundu

Manoharan

2000

Molecular Physics

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Single-crystal variable temperature EPR, optical and polycrystalline magnetic susceptibility studies have been made on a novel six-coordinate Ag(I1) complex. Temperature dependent EPR studies on pure single crystals of this compound reveal that dynamic Jahn-Teller distortion operates above 230 K, between 230 K and 120 K static Jahn-Teller distortion sets in and below 1 10 K there is evidence of exchange interaction. Crystal g values were obtained by least-squares fitting with the data obtained from the orientation dependent EPR spectra of the undiluted single crystal of this complex at 300 K and 77 K . From a n optical study the JahnTeller stabilization energy is found to be -2250cm-'. Comparison of Abs,,, values for other silver(I1) compounds enables us to conclude that the formal geometry of this complex is a tetragonally distorted octahedral. Infrared spectra of this complex were also recorded over a wide range of temperature. Magnetic susceptibility measurements over a wide range of temperature on the powder sample of this compound reveal that the complex is antiferromagnetically coupled in the temperature range 5-40 K with 2J = 0.906cm-', and above 40K it is ferromagnetically coupled with 25 = f7.4cm-'. The effective magnetic moment ( p e r ) of this complex has been compared with that of a series of other silver(I1) complexes available in the literature. Finally, the spectral and magnetic data of this complex have been compared with those of a corresponding isostructural and isomorphous copper(I1) complex.

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“…The situation is different for the other coinage metals, in that Cu, the lighter homologue of Ag, can easily adopt the oxidation state + 2, whereas the heavier homologue Au is mainly found with the oxidation state + 3. Ag 2+ forms stable complexes with a variety of nitrogen donor ligands, such as pyridine [2] or pyrazine (pyz). [3] Other examples of Ag II compounds are the binary fluoride AgF 2 and its complex salts, for example, Cs 2 AgF 4 , [4] which has recently attracted great interest since it orders ferromagnetically at low temperatures.…”

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Strong One‐Dimensional Antiferromagnetic Interactions of Silver(II) Ions in Silver Sulfate

Köhler

2010

Angew Chem Int Ed

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magnetic properties · oxides · silver · solid-state structures · sulfatesThe search for new compounds that contain elements in unusual oxidation states is worthwhile, since these compounds often exhibit novel and unconventional chemical and physical properties, for example, those observed in the superconducting Cu II,III oxides. [1] The dominant oxidation state of Ag is + 1 and only a few compounds with Ag in higher oxidation states have been synthesized to date. The situation is different for the other coinage metals, in that Cu, the lighter homologue of Ag, can easily adopt the oxidation state + 2, whereas the heavier homologue Au is mainly found with the oxidation state + 3. Ag 2+ forms stable complexes with a variety of nitrogen donor ligands, such as pyridine [2] or pyrazine (pyz). [3] Other examples of Ag II compounds are the binary fluoride AgF 2 and its complex salts, for example, Cs 2 AgF 4 , [4] which has recently attracted great interest since it orders ferromagnetically at low temperatures.[5] Among fluorides, even higher oxidation states of Ag are known, for example, Ag 3+ and Ag 4+ in KAgF 4[6] and Cs 2 AgF 6 , [7] respectively. Oxides containing Ag in an oxidation state higher than + 1 are very rare. The binary compound AgO is not a Ag II compound, but the diamagnetic mixed-valent compound Ag I Ag III O 2 . [8] Ag 3 O 4 is also a mixed-valent compound as indicated by the formula Ag II Ag III 2 O 4 , [9] whereas Ag 2 O 3 contains only Ag 3+ ions. [10] Malinowski et al. [11] recently reported the synthesis of black AgSO 4 , which has been obtained by a methathetic reaction of Ag(SbF 6 ) 2 + K 2 SO 4 in anhydrous HF at around À80 8C or by the reaction of AgF 2 with H 2 SO 4 at À35 8C. According to thermoanalytical studies, the product is metastable and decomposes above 120 8C with evolution of O 2 . The triclinic crystal structure of AgSO 4 contains planar rectangular AgO 4 units that are connected by SO 4 tetrahedra to form a three-dimensional network (Figure 1). The Ag-O distances within the AgO 4 units range from 2.09 to 2.20 , [12] as expected for a four-coordinate Ag 2+ ion, [9] thus suggesting that AgSO 4 is indeed a complex Ag II oxide. The two Ag(1)O 4 and Ag(2)O 4 units are significantly elongated along the twofold axes with O-O distances of 2.62 and 2.70 for the short edges and 3.30 and 3.34 for the long edges, respectively. The structural chemistry of the 4d ion Ag 2+ (4d 9 , S = 1/2) differs considerably from that of its 3d and 5d analogues Cu 2+ (3d 9 , S = 1/2) and Au 2+ (5d 9 , S = 1/2). This difference is most obvious when the sulfates are compared. The Ag 2+ ions in AgSO 4 display a rectangular coordination of O atoms, whereas the smaller Cu 2+ ions in CuSO 4 exhibit a distorted octahedral coordination; [13] it is clear that the Jahn-Teller effect is stronger for Ag 2+ than for Cu 2+ . In the structure of AuSO 4 , diamagnetic Au-Au dumbbells with short Au-Au distances of 249 pm are found, [14] thus reflecting the increasing tendency for the occurrence of metal-metal bonding down a gr...

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Electron Paramagnetic Resonance of Dipyridyl-Coordinated Ag2+(4d9)

Cited by 25 publications

References 5 publications

Characterization of the Antiferromagnetism in Ag(pyz)₂(S₂O₈) (pyz = Pyrazine) with a Two-Dimensional Square Lattice of Ag²⁺ Ions

Characterization of the Antiferromagnetism in Ag(pyz)₂(S₂O₈) (pyz = Pyrazine) with a Two-Dimensional Square Lattice of Ag²⁺ Ions

Presence of Jahn-Teller distortions in a novel six-coordinate Ag(II) complex: temperature dependent EPR, optical and magnetic susceptibility measurements

Strong One‐Dimensional Antiferromagnetic Interactions of Silver(II) Ions in Silver Sulfate

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Electron Paramagnetic Resonance of Dipyridyl-Coordinated Ag2+(4d9)

Cited by 25 publications

References 5 publications

Characterization of the Antiferromagnetism in Ag(pyz)2(S2O8) (pyz = Pyrazine) with a Two-Dimensional Square Lattice of Ag2+ Ions

Characterization of the Antiferromagnetism in Ag(pyz)2(S2O8) (pyz = Pyrazine) with a Two-Dimensional Square Lattice of Ag2+ Ions

Presence of Jahn-Teller distortions in a novel six-coordinate Ag(II) complex: temperature dependent EPR, optical and magnetic susceptibility measurements

Strong One‐Dimensional Antiferromagnetic Interactions of Silver(II) Ions in Silver Sulfate

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Characterization of the Antiferromagnetism in Ag(pyz)₂(S₂O₈) (pyz = Pyrazine) with a Two-Dimensional Square Lattice of Ag²⁺ Ions

Characterization of the Antiferromagnetism in Ag(pyz)₂(S₂O₈) (pyz = Pyrazine) with a Two-Dimensional Square Lattice of Ag²⁺ Ions