Coordination ability of amino acid hydrazide ligands and their influence on magnetic properties in copper(ii) coordination polymersElectronic supplementary information (ESI) available: 1H and 13C NMR and MS spectra of N,N′-di-l-leucine hydrazide and N,N′-di-l-phenylalanine hydrazide; synthetic procedure for L1 and L2 (Scheme S1); electronic spectra (Fig. S1); geometric parameters of the metal coordination spheres, stacking interactions and hydrogen bonding in 1 and 2 (Tables S1-S4); representati
Newly synthesized amino acid hydrazide ligands ( L1 = N , N ′-di- l -leucine hydrazide; L2 = N , N ′-di- l -phenylalanine hydrazide) have shown excellent reactivity and stability, as well as extraordinary coordination ability. Reactions of L1 / L2 with copper( ii ) ions and 4,4′-bipyridine (4,4′-bpy...
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Zusammenfassung: | Newly synthesized amino acid hydrazide ligands (
L1
=
N
,
N
′-di-
l
-leucine hydrazide;
L2
=
N
,
N
′-di-
l
-phenylalanine hydrazide) have shown excellent reactivity and stability, as well as extraordinary coordination ability. Reactions of
L1
/
L2
with copper(
ii
) ions and 4,4′-bipyridine (4,4′-bpy) as a secondary spacer yielded new coordination polymers {Cu(L1)
0.5
(4,4′-bpy)(H
2
O)(NO
3
)}
n
·1.5
n
H
2
O (
1
) and {Cu
3
(L2)
2
(4,4′-bpy)(H
2
O)
2
}
n
(NO
3
)
2
n
·3
n
H
2
O (
2
). UV/vis spectroscopy together with structural analysis showed that the deprotonated ligands
L1
2−
/
L2
2−
with six available donor atoms per ligand have the ability for strong chelation to copper(
ii
) ions, acting as bis-bidentate (
L1
2−
) and bridging bi + tridentate (
L2
2−
) ligands. Compound
1
contains copper(
ii
) ions simultaneously bridged with short hydrazide bridges (4.725 Å) and long 4,4′-bpy spacers (11.144 Å) forming a two-dimensional coordination network. In compound
2
, a pair of
L2
2−
molecules bridges three copper(
ii
) ions, which are further interconnected with 4,4′-bpy into an overall one-dimensional chain-like structure. Although bulkier, the phenylalanine ligand (
L2
) was found to be more flexible compared to the leucine ligand (
L1
), exhibiting additional intramolecular contact: cation-π interaction. In both compounds, the hydrazide (-N-N-) bridge mediates the antiferromagnetic interaction between copper(
ii
) ions. Hydrogen bonds have a strong influence on the crystal packing and physical (magnetic) properties. The reported compounds are first examples of hydrazide-bridged metal centres featuring amino acid-based ligands.
Copper(
ii
) coordination polymers constructed from newly synthesized amino acid hydrazides and 4,4′-bipyridine exhibit antiferromagnetic ordering mediated through hydrazide bridges. |
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ISSN: | 1466-8033 |
DOI: | 10.1039/c8ce00210j |