Synthesis, crystal structure, and magnetic properties of two-dimensional divalent metal glutarate/dipyridylamine coordination polymers, with a single crystal-to-single crystal transformation in the copper derivative

Journal Article · Thu Jan 15 04:00:00 EST 2009 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2008.09.020· OSTI ID:21212149

Montney, Matthew R ^[1]; Supkowski, Ronald M ^[2]; Staples, Richard J ^[1]

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1. Lyman Briggs College and Department of Chemistry, Michigan State University, East Lansing, MI 48825 (United States)
2. Department of Chemistry and Physics, King's College, Wilkes-Barre, PA 18711 (United States)

Hydrothermal reaction of divalent metal chlorides with glutaric acid and 4,4'-dipyridylamine (dpa) has afforded an isostructural family of coordination polymers with formulation [M(glu)(dpa)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate). Square pyramidal coordination is seen in 1-3, with semi-ligation of a sixth donor to produce a '5+1' extended coordination sphere. Neighboring metal atoms are linked into 1D [M(glu)]{sub n} neutral chains through chelating/monodentate bridging glutarate moieties with a syn-anti binding mode, and semi-chelation of the pendant carboxylate oxygen. These chains further connect into 2D layers through dipodal dpa ligands. Neighboring layers stack into the pseudo 3D crystal structure of 1-3 through supramolecular hydrogen bonding between dpa amine units and the semi-chelated glutarate oxygen atoms. The variable temperature magnetic behavior of 1-3 was explored and modeled as infinite 1D Heisenberg chains. Notably, complex 3 undergoes a thermally induced single crystal-to-single crystal transformation between centric and acentric space groups, with a conformationally disordered unilayer structure at 293 K and an ordered bilayer structure at 173 K. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analyses. - Graphical abstract: The coordination polymers [M(glu)(dpa)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate, dpa=4,4'-dipyridylamine) exhibit 2D layer structures based on 1D [M(glu)]{sub n} chains linked through dpa tethers. Antiferromagnetic coupling is observed for 2 and 3, while ferromagnetism is predominant in 1. Compound 3 undergoes a thermally induced single crystal-to-single crystal transformation from an acentric to a centrosymmetric space group.

• OSTI ID: 21212149
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 182; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTROSCOPY
AMINES
ANTIFERROMAGNETISM
CHELATING AGENTS
CHLORIDES
COBALT COMPLEXES
COPPER COMPLEXES
CRYSTAL STRUCTURE
FERROMAGNETISM
GLUTARIC ACID
INFRARED SPECTRA
LAYERS
LIGANDS
MAGNETIC PROPERTIES
MONOCRYSTALS
NICKEL COMPLEXES
ORGANIC POLYMERS
SPACE GROUPS
SYNTHESIS
THERMAL GRAVIMETRIC ANALYSIS
TRANSFORMATIONS