2-(1H-pyrazol-3-yl)pyrazine: a polytopic N-donor ligand used to construct Cu-[2+2] molecular grid: synthesis, structure, and magnetic properties

Feng, Xuefeng; Yang, Chao; Liao, Zhen-wei; Song, Yu‐Mei; Huang, Hongfeng; Sun, Gong-ming; Luo, Mingbiao; Liu, Shujuan; Luo, Feng

doi:10.1080/00958972.2011.641957

Journal of Coordination Chemistry

2011

DOI: 10.1080/00958972.2011.641957

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2-(1H-pyrazol-3-yl)pyrazine: a polytopic N-donor ligand used to construct Cu-[2+2] molecular grid: synthesis, structure, and magnetic properties

Xuefeng Feng¹,

Chao Yang²,

Zhen-wei Liao³

et al.

Abstract: Herein, we present a new polytopic N-donor, which is used to construct a metal-organic compound. The resulting metal-organic compound, Cu 4 (L) 6 (NO 3 ) 2 (HL¼(1H-pyrazol-3-yl)pyrazine) (1), is synthesized by the hydrothermal reaction of Cu(NO 3 ) 2 and HL (ratio: 1 : 1). Single-crystal X-ray diffraction shows that 1 comprises a Cu-[2þ2] molecular grid. Magnetic studies reveal antiferromagnetic interactions, interpreted by a simplified dinuclear mode.

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A Family of 12‐Azametallacrown‐4 Structural Motif with Heterometallic Mn^III‐Ln‐Mn^III‐Ln (Ln=Dy, Er, Yb, Tb, Y) Alternate Arrangement and Single‐Molecule Magnet Behavior

Yang

Cao

et al. 2015

Chemistry A European J

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Mixed 3d-4f 12-azametallacrown-4 complexes, [Mn2 Ln2 (OH)2 (hppt)4 (OAc)2 (DMF)2 ]⋅2 DMF⋅H2 O [Ln=Dy (1), Er (2), Yb (3), Tb (4) and Y (5), H2 hppt=3-(2-hydroxyphenyl)-5-(pyrazin-2-yl)-1,2,4-triazole)], were synthesized by reactions of H2 hppt with Mn(OAc)2 ⋅4 H2 O and Ln(NO3 )3 ⋅6 H2 O. This is the first 3d-4f azametallacrown family to incorporate Ln ions into the ring sets. These isostructural complexes exhibit alternating arrangements of two Mn and two Ln ions in the rings with each pair of metal centers bound by an NN group and μ2 -O bridging. Magnetic measurements revealed dominant antiferromagnetic interactions between metal centers, and frequency-dependent out-of-phase (${\chi {^\prime}{^\prime}_{\rm{M}} }$) signals below 4 K suggest slow relaxation of magnetization.

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A Family of 12‐Azametallacrown‐4 Structural Motif with Heterometallic Mn^III‐Ln‐Mn^III‐Ln (Ln=Dy, Er, Yb, Tb, Y) Alternate Arrangement and Single‐Molecule Magnet Behavior

Yang

Cao

et al. 2015

Chemistry A European J

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Planar Cu₂(ppz)₂ Dimers as SBUs for Diverse Polyoxometalate-Based Metal Organic Frameworks

Liu

Hou

et al. 2014

Crystal Growth & Design

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Five new polyoxometalate-based metal organic frameworks, [Cu 4 (ppz) 4 (PO 4 )]•[CuBr 2 ] (1), [Cu 4 (ppz) 4 -(MoO 4 ) 2 (H 2 O)]•2H 2 O (2), [Cu(Hppz)(Mo 2 O 7 )] (3), [ C u 2 ( p p z ) 2 ( M o 3 O 1 0 ) ] ( 4 ) , a n d [ C u 6 ( p p z ) 6 -(PMo 3 V Mo 9 VI O 40 )] (5) (Hppz = 2-(1H-pyrazol-3-yl)pyrazine), have been hydrothermally synthesized and fully characterized, in which a planar Cu 2 (ppz) 2 dimer acts as a secondary building unit (SBU) and provides up to six potential binding sites. In virtue of the strong Jahn−Teller (JT) effect of Cu(II) ions, the potential binding sites in the Cu 2 (ppz) 2 SBU can facilely be occupied by auxiliary oxygen-donor anions and/ or outward pyrazine nitrogen atoms of neighboring SBUs. The auxiliary oxygen-donor anions in compounds 1−5 range from simple phosphate and molybdate, zonal Mo 2 O 7 2− and Mo 3 O 10 2− to a spherical three-electron reduced Keggin anion [PMo 12 O 40 ] 6− , respectively. Compound 1 contains an unprecedented 3D (4,6)connected cationic open framework [Cu 4 (ppz) 4 (PO 4 )] + with 1D channels filled by linear CuBr 2 − anions, where the Cu 2 (ppz) 2 SBUs and PO 4 groups act as nodes and the outward Cu−N bonds and oxo bridges act as linkers. 2 possesses a complicated trinodal (3,4)-connected topological framework, in which μ 3 -MoO 4 and Cu 2 (ppz) 2 groups act as 3-and 4-connected nodes and the outward Cu−N bonds and double μ 2 -MoO 4 groups act as linkers. Differing from 1 and 2, compound 3 shows a 2D organic− inorganic hybrid sheet constructed by a [Mo 2 O 7 ] 2− ribbon of cyclic hexameric edge-shared [MoO 6 ]-octahedra and Cu 2 (ppz) 2 SBUs. Similar to 3, compound 4 also shows 2D organic−inorganic hybrid sheets constructed by zigzag [Mo 3 O 10 ] 2− ribbons and Cu 2 (ppz) 2 SBUs, and adjacent sheets are extended by weak Mo−N bonds into the 3D network. 5 has a 3D 6-connected pcu topological framework constructed by Cu 2 (ppz) 2 SBUs and [PMo 12 O 40 ] 6− anions, which also can be viewed as cationic of the NbO topological [Cu 6 (ppz) 6 ] 6+ network with cavities filled by [PMo 12 O 40 ] 6− anions. Magnetic measurements show that there is strong antiferromagnetic coupling within the Cu 2 (ppz) 2 dimer and only one unpaired electron within the three-electron reduced Keggin anion.

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Structural and spectroscopic insights on the coordination chemistry of the rigid heterotopic chelating ligand 1H-pyrazolo[4,3-h]quinoline

Goodwin

Kruger

Hawes

2021

Journal of Coordination Chemistry

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2-(1H-pyrazol-3-yl)pyrazine: a polytopic N-donor ligand used to construct Cu-[2+2] molecular grid: synthesis, structure, and magnetic properties

Cited by 3 publications

References 16 publications

A Family of 12‐Azametallacrown‐4 Structural Motif with Heterometallic Mn^III‐Ln‐Mn^III‐Ln (Ln=Dy, Er, Yb, Tb, Y) Alternate Arrangement and Single‐Molecule Magnet Behavior

A Family of 12‐Azametallacrown‐4 Structural Motif with Heterometallic Mn^III‐Ln‐Mn^III‐Ln (Ln=Dy, Er, Yb, Tb, Y) Alternate Arrangement and Single‐Molecule Magnet Behavior

Planar Cu₂(ppz)₂ Dimers as SBUs for Diverse Polyoxometalate-Based Metal Organic Frameworks

Structural and spectroscopic insights on the coordination chemistry of the rigid heterotopic chelating ligand 1H-pyrazolo[4,3-h]quinoline

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2-(1H-pyrazol-3-yl)pyrazine: a polytopic N-donor ligand used to construct Cu-[2+2] molecular grid: synthesis, structure, and magnetic properties

Cited by 3 publications

References 16 publications

A Family of 12‐Azametallacrown‐4 Structural Motif with Heterometallic MnIII‐Ln‐MnIII‐Ln (Ln=Dy, Er, Yb, Tb, Y) Alternate Arrangement and Single‐Molecule Magnet Behavior

A Family of 12‐Azametallacrown‐4 Structural Motif with Heterometallic MnIII‐Ln‐MnIII‐Ln (Ln=Dy, Er, Yb, Tb, Y) Alternate Arrangement and Single‐Molecule Magnet Behavior

Planar Cu2(ppz)2 Dimers as SBUs for Diverse Polyoxometalate-Based Metal Organic Frameworks

Structural and spectroscopic insights on the coordination chemistry of the rigid heterotopic chelating ligand 1H-pyrazolo[4,3-h]quinoline

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A Family of 12‐Azametallacrown‐4 Structural Motif with Heterometallic Mn^III‐Ln‐Mn^III‐Ln (Ln=Dy, Er, Yb, Tb, Y) Alternate Arrangement and Single‐Molecule Magnet Behavior

A Family of 12‐Azametallacrown‐4 Structural Motif with Heterometallic Mn^III‐Ln‐Mn^III‐Ln (Ln=Dy, Er, Yb, Tb, Y) Alternate Arrangement and Single‐Molecule Magnet Behavior

Planar Cu₂(ppz)₂ Dimers as SBUs for Diverse Polyoxometalate-Based Metal Organic Frameworks