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

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.

Substituent effects in 4-connected zinc isophthalate coordination polymers with a pyridylnicotinamide ligand: From dimer-based layers to ribbons with embedded infinite water molecule chains

“…The resulting close stacking of neighboring [Zn(ip)(3-pna)] n layers does not provide any solvent-accessible void space within the interlamellar regions. The overall topology and structure of 1 is similar to that observed in the recently prepared copper analog [Cu(ip)(3-pna)] n [28].…”

Effect of Nitrogen Donor Disposition on Topology in Cobalt Isophthalate Coordination Polymers Containing Dipyridylamide Ligands

“…{[Co(hip)(dpp)] · H 2 O} n shows a fourfold interpenetrated diamondoid topology, while its nickel derivative [Ni(hip)(dpp) 1.5 (H 2 O)] n displays interdigitated sets of 1D ribbon motifs 21. In comparison to the commercially available bpy, dpe, and dpp ligands, the kinked dipyridylamides 3‐pyridylisonicotinamide (3‐pina, Scheme ) and 4‐pyridylmethylisonicotinamide (4‐pmina, Scheme ) have been utilized much less frequently as a coligand for the construction of coordination polymers 22–26…”

“…{[Cu(ip)(3‐pina)] · H 2 O} n exhibits {Cu 2 (OCO) 2 } dimeric units connected into a non‐interpenetrated 3‐D 6 5 8 cds network. Both [Cu(mip)(3‐pina)] n and [Cu(meoip)(3‐pina)] n display dimer‐based 4 12 6 3 pcu networks 22. The internal amide functional groups of 3‐pina or 4‐pmina can provide both hydrogen bonding donor and acceptor groups, offering the potential of multiple structure‐directing supramolecular interactions during self‐assembly.…”

Metal‐ and Substituent‐Dependent Structural Diversity in ­Cobalt and Nickel Isophthalate Coordination Polymers with Bis(4‐pyridylformyl)piperazine Tethers

“…{[Cu(ip)(3‐pina)] · H 2 O} n (3‐pina = 3‐pyridylisonicotinamide) exhibits {Cu 2 (OCO) 2 } dimeric units connected into a non‐interpenetrated 3D 4‐connected 6 5 8 cds network. Both [Cu(mip)(3‐pina)] n (mip = 5‐methylisophthalate, Scheme ) and [Cu(omeip)(3‐pina)] n (omeip = 5‐methoxyisophthalate, Scheme ) display dimer‐based 3D 6‐connected 4 12 6 3 pcu networks in contrast 13. Synthetic conditions during self‐assembly of substituted isophthalate coordination polymers can result in dramatically different topologies.…”