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Carbon dioxide uptake by [Cu(bpca)] + : synthesis, crystal structure, and magnetic properties of {[Na(H 2 O) 2 ][Cu 2 (bpca) 2 (CO 3 )(HCO 3 )]} n [Hbpca = bis(2-pyridylcarbonyl)amide]
Ist Teil von
New journal of chemistry, 2023-01, Vol.47 (3), p.1066-1075
Ort / Verlag
Cambridge: Royal Society of Chemistry
Erscheinungsjahr
2023
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
Herein we report on the preparation, spectroscopic and thermal characterization, structural study, and magnetic investigation of a new heterobimetallic coordination polymer (CP) of formula {[Na(H
2
O)
2
][Cu
2
(bpca)
2
(CO
3
)(HCO
3
)]}
n
(1) [Hbpca = bis(2-pyridylcarbonyl)amide], which was isolated through the fixation of aerial carbon dioxide by the preformed [Cu(bpca)]
+
complex in basic water/DMSO solvent mixtures. Compound 1 is made up of neutral heterobimetallic zigzag chains growing parallel to the crystallographic
c
axis where carbonate, bicarbonate, and bpca anions act as bridges with regular alternation of a pair of [Cu(bpca)]
+
units and one [Na(H
2
O)
2
]
+
fragment. The two crystallographically independent copper(
ii
) ions (Cu1 and Cu2) are five-coordinate in somewhat distorted square pyramidal surroundings with three nitrogen atoms from the bpca ligand and either one bicarbonate-oxygen (Cu1) or a carbonate-oxygen (Cu2) in the basal plane and a shared carbonate-oxygen atom (Cu1 and Cu2) in the apical position. Each sodium(
i
) ion is also five-coordinate in a distorted trigonal bipyramidal environment, with two oxygen atoms from a bpca ligand and a water molecule building the trigonal plane and a bicarbonate-oxygen and another water molecule in the axial sites. The intrachain copper–copper separation across the bridging carbonate is 4.109(1) Å. The cryomagnetic study of 1 reveals the occurrence of a weak ferromagnetic interaction between the copper(II) ions through the bridging carbonate [
J
= +0.17(4) cm
−1
, the spin Hamiltonian being defined as
H
=
−J
S
Cu1
·
S
Cu2
]. Density functional theory (DFT) calculations on the [{Cu(bpca)}
2
(μ-CO
3
)] fragment of
1
in the gas phase and solid state were used to estimate the magnetic coupling constant (
J
= +0.42 cm
−1
) and to describe the electronic structure and magnetic topology of the system.