Halo and azido copper(II) coordination polymers featuring the gem-diolate forms of di-2-pyridyl ketone

Harikleia Sartzi; Giannis S. Papaefstathiou; Vassilis Psycharis; Albert Escuer; Spyros P. Perlepes; Constantinos C. Stoumpos

doi:10.1016/j.poly.2009.06.016

Halo and azido copper(II) coordination polymers featuring the gem-diolate forms of di-2-pyridyl ketone

Harikleia Sartzi, Giannis S. Papaefstathiou, Vassilis Psycharis, Albert Escuer, Spyros P. Perlepes, Constantinos C. Stoumpos

Chemistry

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

Abstract

The reactions of di-2-pyridyl ketone, (py)₂CO, with [Cu ₂(O₂CMe)₄(H₂O)₂] in the presence of NaN₃, HCl and HBr have led to the isolation of complexes [[Cu₈((Py)₂CO₂J₄(N ₃)N₃₆(O₂CMe)₂]2MeCN. H₂O)∞ (1.2MeCN·H₂O), [Cu₂{(Py) ₂C(OH)O)Cl₃]∞ (2) and [Cu2[(Py)₂C(OH) OJBr₃]∞ (3), respectively, where (Py)₂CO ₂^2- and (py)₂;pC(OH)O- are the dianion and the monoanion of the gem-diol form of (Py)₂CO. Complex 1.2MeCN.H ₂O is an ID coordination polymer consisting of centrosymmetric [Cu₈{(py)₂CO₂}₄ (N₃) ₆(O₂CMe)₂] cluster units linked through weakly coordinated azido bridges. The (Py)₂CO₂^2- groups adopt the η¹:η²:η²: η₄ coordination mode, while the N₃^- ions behave as η² and η : η :μ₃ ligands. The isostructural compounds 2 and 3 are also ID coordination polymers consisting of {Cu₂{(py)₂C (OH)O)X₃}₂ units (X-Cl, Br) linked through double halo bridges. The (py)₂C(OH)O^- ligand adopts the tridentate, bis-chelating η¹:η²: η²:μ mode. A common feature in the three complexes is the presence of interchain H-bonding interactions which result in the formation of 2D networks. The magnetic properties of 1-3 have been studied by variable-temperature dc magnetic susceptibility and variable-field magnetization techniques. The analyses of the magnetic data were performed taking into account only the dominant exchange interactions within dinuclear subunits. The intradinuclear exchange interactions have been found to vary from strongly and moderately antiferromagnetic in 1 to ferromagnetic in 2 and 3. This work demonstrates the flexibility, versatility and synthetic potential of combining (py)₂CO with carboxylate and azido or halo ligands.

Original language	English (US)
Pages (from-to)	100-109
Number of pages	10
Journal	Polyhedron
Volume	29
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2009.06.016
State	Published - Jan 13 2010

Keywords

Copper(II) complexes
Crystal structures
Di-2-pyridyl ketone
Magnetic properties
One-dimensional coordination polymers

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.poly.2009.06.016

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@article{6e80e96cf46148d3afded01cf743db34,

title = "Halo and azido copper(II) coordination polymers featuring the gem-diolate forms of di-2-pyridyl ketone",

abstract = "The reactions of di-2-pyridyl ketone, (py)2CO, with [Cu 2(O2CMe)4(H2O)2] in the presence of NaN3, HCl and HBr have led to the isolation of complexes [[Cu8((Py)2CO2J4(N 3)N36(O2CMe)2]2MeCN. H2O)∞ (1.2MeCN·H2O), [Cu2{(Py) 2C(OH)O)Cl3]∞ (2) and [Cu2[(Py)2C(OH) OJBr3]∞ (3), respectively, where (Py)2CO 22- and (py)2;pC(OH)O- are the dianion and the monoanion of the gem-diol form of (Py)2CO. Complex 1.2MeCN.H 2O is an ID coordination polymer consisting of centrosymmetric [Cu8{(py)2CO2}4 (N3) 6(O2CMe)2] cluster units linked through weakly coordinated azido bridges. The (Py)2CO22- groups adopt the η1:η2:η2: η4 coordination mode, while the N3- ions behave as η2 and η : η :μ3 ligands. The isostructural compounds 2 and 3 are also ID coordination polymers consisting of {Cu2{(py)2C (OH)O)X3}2 units (X-Cl, Br) linked through double halo bridges. The (py)2C(OH)O- ligand adopts the tridentate, bis-chelating η1:η2: η2:μ mode. A common feature in the three complexes is the presence of interchain H-bonding interactions which result in the formation of 2D networks. The magnetic properties of 1-3 have been studied by variable-temperature dc magnetic susceptibility and variable-field magnetization techniques. The analyses of the magnetic data were performed taking into account only the dominant exchange interactions within dinuclear subunits. The intradinuclear exchange interactions have been found to vary from strongly and moderately antiferromagnetic in 1 to ferromagnetic in 2 and 3. This work demonstrates the flexibility, versatility and synthetic potential of combining (py)2CO with carboxylate and azido or halo ligands.",

keywords = "Copper(II) complexes, Crystal structures, Di-2-pyridyl ketone, Magnetic properties, One-dimensional coordination polymers",

author = "Harikleia Sartzi and Papaefstathiou, {Giannis S.} and Vassilis Psycharis and Albert Escuer and Perlepes, {Spyros P.} and Stoumpos, {Constantinos C.}",

year = "2010",

month = jan,

day = "13",

doi = "10.1016/j.poly.2009.06.016",

language = "English (US)",

volume = "29",

pages = "100--109",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Limited",

number = "1",

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TY - JOUR

T1 - Halo and azido copper(II) coordination polymers featuring the gem-diolate forms of di-2-pyridyl ketone

AU - Sartzi, Harikleia

AU - Papaefstathiou, Giannis S.

AU - Psycharis, Vassilis

AU - Escuer, Albert

AU - Perlepes, Spyros P.

AU - Stoumpos, Constantinos C.

PY - 2010/1/13

Y1 - 2010/1/13

N2 - The reactions of di-2-pyridyl ketone, (py)2CO, with [Cu 2(O2CMe)4(H2O)2] in the presence of NaN3, HCl and HBr have led to the isolation of complexes [[Cu8((Py)2CO2J4(N 3)N36(O2CMe)2]2MeCN. H2O)∞ (1.2MeCN·H2O), [Cu2{(Py) 2C(OH)O)Cl3]∞ (2) and [Cu2[(Py)2C(OH) OJBr3]∞ (3), respectively, where (Py)2CO 22- and (py)2;pC(OH)O- are the dianion and the monoanion of the gem-diol form of (Py)2CO. Complex 1.2MeCN.H 2O is an ID coordination polymer consisting of centrosymmetric [Cu8{(py)2CO2}4 (N3) 6(O2CMe)2] cluster units linked through weakly coordinated azido bridges. The (Py)2CO22- groups adopt the η1:η2:η2: η4 coordination mode, while the N3- ions behave as η2 and η : η :μ3 ligands. The isostructural compounds 2 and 3 are also ID coordination polymers consisting of {Cu2{(py)2C (OH)O)X3}2 units (X-Cl, Br) linked through double halo bridges. The (py)2C(OH)O- ligand adopts the tridentate, bis-chelating η1:η2: η2:μ mode. A common feature in the three complexes is the presence of interchain H-bonding interactions which result in the formation of 2D networks. The magnetic properties of 1-3 have been studied by variable-temperature dc magnetic susceptibility and variable-field magnetization techniques. The analyses of the magnetic data were performed taking into account only the dominant exchange interactions within dinuclear subunits. The intradinuclear exchange interactions have been found to vary from strongly and moderately antiferromagnetic in 1 to ferromagnetic in 2 and 3. This work demonstrates the flexibility, versatility and synthetic potential of combining (py)2CO with carboxylate and azido or halo ligands.

AB - The reactions of di-2-pyridyl ketone, (py)2CO, with [Cu 2(O2CMe)4(H2O)2] in the presence of NaN3, HCl and HBr have led to the isolation of complexes [[Cu8((Py)2CO2J4(N 3)N36(O2CMe)2]2MeCN. H2O)∞ (1.2MeCN·H2O), [Cu2{(Py) 2C(OH)O)Cl3]∞ (2) and [Cu2[(Py)2C(OH) OJBr3]∞ (3), respectively, where (Py)2CO 22- and (py)2;pC(OH)O- are the dianion and the monoanion of the gem-diol form of (Py)2CO. Complex 1.2MeCN.H 2O is an ID coordination polymer consisting of centrosymmetric [Cu8{(py)2CO2}4 (N3) 6(O2CMe)2] cluster units linked through weakly coordinated azido bridges. The (Py)2CO22- groups adopt the η1:η2:η2: η4 coordination mode, while the N3- ions behave as η2 and η : η :μ3 ligands. The isostructural compounds 2 and 3 are also ID coordination polymers consisting of {Cu2{(py)2C (OH)O)X3}2 units (X-Cl, Br) linked through double halo bridges. The (py)2C(OH)O- ligand adopts the tridentate, bis-chelating η1:η2: η2:μ mode. A common feature in the three complexes is the presence of interchain H-bonding interactions which result in the formation of 2D networks. The magnetic properties of 1-3 have been studied by variable-temperature dc magnetic susceptibility and variable-field magnetization techniques. The analyses of the magnetic data were performed taking into account only the dominant exchange interactions within dinuclear subunits. The intradinuclear exchange interactions have been found to vary from strongly and moderately antiferromagnetic in 1 to ferromagnetic in 2 and 3. This work demonstrates the flexibility, versatility and synthetic potential of combining (py)2CO with carboxylate and azido or halo ligands.

KW - Copper(II) complexes

KW - Crystal structures

KW - Di-2-pyridyl ketone

KW - Magnetic properties

KW - One-dimensional coordination polymers

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DO - 10.1016/j.poly.2009.06.016

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VL - 29

SP - 100

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JO - Polyhedron

JF - Polyhedron

IS - 1

ER -

Halo and azido copper(II) coordination polymers featuring the gem-diolate forms of di-2-pyridyl ketone

Abstract

Keywords

ASJC Scopus subject areas

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