TY - JOUR
T1 - Polynuclear and coordination polymers of copper(II) complexes assembled by flexible polyamines and bridging rigid N-heterocyclic multicarboxylates
AU - Louka, Febee R.
AU - Haq, Sabrina J.
AU - Guidry, Hollie R.
AU - Williams, Bailey R.
AU - Henary, Maher M.
AU - Fischer, Roland
AU - Torvisco Gomez, Ana
AU - Massoud, Salah S.
AU - Mautner, Franz-Andreas
PY - 2020/1/24
Y1 - 2020/1/24
N2 - Four trinuclear Cu(II) complexes bridged by N-heterocyclic multicarboxylic acids: [Cu
3(dien)
2(μ
2-Pz
3,5-dc)
2(H
2O)
2]·4H
2O (1), [Cu
3(pmdien)
2(μ
2-Py
2,5-dc)
2(ClO
4)
2(H
2O)
2] (2), [Cu
3(trpn)
2(μ
2-Py
2,5-dc)
2(ClO
4)
2] (3) and [Cu
3(ip
3tren)
2(μ
2-Py
2,4-dc)
2(H
2O)](ClO
4)
2 (4) and the coordination polymer: catena-[Cu
2(bedmpza)
2(μ
2-Py
2,4-dc)](ClO
4)
2·H
2O (5) as well as the monomeric [Cu(bdmpzpy)(Py
2,6-dc)]
2·3H
2O (6), where H
3Pz
3,5-dc = 3,5-pyrazole dicarboxylic acid, H
2Py
2,4-dc = 2,4-pyridine dicarboxylic acid, H
2Py
2,5-dc = 2,5-pyridine dicarboxylic acid, H
2Py
2,6-dc = 2,6-pyridine dicarboxylic, dien = diethylenetriamine, pmedien = N,N,N′,N″,N″-pentamethyldiethylene-triamine, bedmpza = bis(3,5-dimethylpyrazolyl-1H-ethyl)amine, trpn = tris(3-aminopropyl)amine, ip
3tren = tris(2-isopropyl-2-ethyl)amine and bdmpzpy = 2,6-bis[(3,5-dimethyl-1H-pyrazolyl)methyl]pyridine were synthesized. The compounds were structurally characterized by elemental microanalyses, IR and UV–Vis spectra as well as by single crystal X-ray crystallography for 1–3, 5 and 6. In 1–3 and 5, the N-heterocyclic multicarboxylate dianion linkers are simultaneously bound by at least one N,O chelating hetero-aromatic dicarboxylato anions via ring-N atom and one O-atom of the adjacent carboxylato group and an O-atom of the carboxylates located at the other side of the heteroxyclic ring. In complex 6 the adjacent bdmpzpy ligands constitute π-π interactions through the central pyridine rings with separation of the centers of gravities = 3.666(2) Å. The degree of nuclearity in the polynuclear species depends entirely on the skeletal structure of the linker N-heterocyclic multicarboxylic acids and the amine coligands.
AB - Four trinuclear Cu(II) complexes bridged by N-heterocyclic multicarboxylic acids: [Cu
3(dien)
2(μ
2-Pz
3,5-dc)
2(H
2O)
2]·4H
2O (1), [Cu
3(pmdien)
2(μ
2-Py
2,5-dc)
2(ClO
4)
2(H
2O)
2] (2), [Cu
3(trpn)
2(μ
2-Py
2,5-dc)
2(ClO
4)
2] (3) and [Cu
3(ip
3tren)
2(μ
2-Py
2,4-dc)
2(H
2O)](ClO
4)
2 (4) and the coordination polymer: catena-[Cu
2(bedmpza)
2(μ
2-Py
2,4-dc)](ClO
4)
2·H
2O (5) as well as the monomeric [Cu(bdmpzpy)(Py
2,6-dc)]
2·3H
2O (6), where H
3Pz
3,5-dc = 3,5-pyrazole dicarboxylic acid, H
2Py
2,4-dc = 2,4-pyridine dicarboxylic acid, H
2Py
2,5-dc = 2,5-pyridine dicarboxylic acid, H
2Py
2,6-dc = 2,6-pyridine dicarboxylic, dien = diethylenetriamine, pmedien = N,N,N′,N″,N″-pentamethyldiethylene-triamine, bedmpza = bis(3,5-dimethylpyrazolyl-1H-ethyl)amine, trpn = tris(3-aminopropyl)amine, ip
3tren = tris(2-isopropyl-2-ethyl)amine and bdmpzpy = 2,6-bis[(3,5-dimethyl-1H-pyrazolyl)methyl]pyridine were synthesized. The compounds were structurally characterized by elemental microanalyses, IR and UV–Vis spectra as well as by single crystal X-ray crystallography for 1–3, 5 and 6. In 1–3 and 5, the N-heterocyclic multicarboxylate dianion linkers are simultaneously bound by at least one N,O chelating hetero-aromatic dicarboxylato anions via ring-N atom and one O-atom of the adjacent carboxylato group and an O-atom of the carboxylates located at the other side of the heteroxyclic ring. In complex 6 the adjacent bdmpzpy ligands constitute π-π interactions through the central pyridine rings with separation of the centers of gravities = 3.666(2) Å. The degree of nuclearity in the polynuclear species depends entirely on the skeletal structure of the linker N-heterocyclic multicarboxylic acids and the amine coligands.
KW - Bridged carboxylate
KW - Coordination polymer
KW - Copper
KW - Crystal structures
KW - Polynuclear complexes
UR - http://www.scopus.com/inward/record.url?scp=85074768778&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2019.119240
DO - 10.1016/j.ica.2019.119240
M3 - Article
SN - 0020-1693
VL - 500
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
M1 - 119240
ER -