Dipyridylamide Donor Disposition and Isophthalate Substituent Steric Effect on the Dimensionality and Topology of Divalent Copper Coordination Polymers |
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Authors: | Megan E O'Donovan Angela R Porta Maria D Torres Salgado Robert L LaDuca |
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Institution: | Lyman Briggs College and Department of Chemistry, Michigan State University, East Lansing, MI 48825 USA |
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Abstract: | 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 {Cu2(OCO)2} dimeric units. {Cu(ip)(3‐pina)]·H2O}n ( 2 , 3‐pina = 3‐pyridylisonicotinamide) exhibits similar dimeric units, but in contrast to 1 these are connected into a non‐interpenetrated 3D 658 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 41263 pcu networks in contrast to 2 . Use of 5‐hydroxyisophthalate (H2hip) as a precursor afforded a mixture of {Cu2(hip)2(3‐pina)4]·9.5H2O}n ( 5 ) and Cu(hip)(3‐pina)]n ( 6 ). Compound 5 shows a 2D interdigitated structure with Cu(hip)]n coordination polymer layers featuring {Cu2(OCO)2} dimeric units and pendant 3‐pina ligands, while 6 also showed a dimer‐based 41263 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)]·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 {Cu2(OCO)2} dimeric units in 1 . Thermal decomposition behavior is also discussed. |
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Keywords: | Hydrothermal synthesis Copper Antiferromagnetism Coordination polymers X‐ray diffraction |
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