Dipyridylamide Donor Disposition and Isophthalate Substituent Steric Effect on the Dimensionality and Topology of Divalent Copper Coordination Polymers

作者：O'Donovan Megan E; Porta Angela R; Salgado Maria D Torres; LaDuca Robert L^*

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2014, 640(11): 2113-2122.

DOI：10.1002/zaac.201400303

• Hydrothermal synthesis
• Copper
• Antiferromagnetism
• Coordination polymers
• X-ray diffraction

Divalent copper coordination polymers containing an isophthalate ligand and a dipyridylamide ligand show different dimensionalities and topologies depending on pyridyl nitrogen donor disposition and the steric bulk of the substituent on the dicarboxylate aromatic ring. According to single-crystal X-ray diffraction, [Cu(ip)(3-pna)](n) (1, ip = isophthalate, 3-pna = 3-pyridylnicotinamide) shows a (4, 4) layered grid structure based on {Cu-2(OCO)(2)} dimeric units. {[Cu(ip)(3-pina)]center dot H2O}(n) (2, 3-pina = 3-pyridylisonicotinamide) exhibits similar dimeric units, but in contrast to 1 these are connected into a non-interpenetrated 3D 6(5)8 cds network. Both [Cu(mip)(3-pina)](n) (3, mip = 5-methylisophthalate) and [Cu(meoip)(3-pina)](n) (4, mip = 5-methoxyisophthalate) display dimer-based 4(12)6(3) pcu networks in contrast to 2. Use of 5-hydroxyisophthalate (H(2)hip) as a precursor afforded a mixture of {[Cu-2(hip)(2)(3-pina)(4)]center dot 9.5H(2)O}(n) (5) and [Cu(hip)(3-pina)](n) (6). Compound 5 shows a 2D interdigitated structure with [Cu(hip)](n) coordination polymer layers featuring {Cu-2(OCO)(2)} dimeric units and pendant 3-pina ligands, while 6 also showed a dimer-based 4(12)6(3) pcu network. Use of the very sterically bulky 5-tert-butylisophthalate (tbip) ligand afforded the 1D chain coordination polymer {[Cu(tbip)(3-pina)(2)(H2O)]center dot H2O}(n) (7), which contains isolated copper ions in contrast to 1-6, and has a curious butterfly resemblance. Very weak antiferromagnetic coupling is seen within the {Cu-2(OCO)(2)} dimeric units in 1. Thermal decomposition behavior is also discussed.

• 出版日期2014-9