Magneto-structural studies of two new cobalt(ii)-N,N-diisobutylisonicotinamide compounds: [CoLCl2]n and [Co(L)2(H2O)4][CoLBr3]2·2H2OElectronic supplementary information (ESI) available: CCDC reference numbers 808174-808175. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c1dt10991j
Two similar synthetic pathways using the ligand N , N -diisobutylisonicotinamide (L) with anhydrous CoX 2 salts (being X = Cl − , Br − ) led to different species: a one-dimensional system, [CoLCl 2 ] n , 1 , and an ionic product [Co(L) 2 (H 2 O) 4 ][CoLBr 3 ] 2 ·2H 2 O, 2 , respectively. Compound 1...
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Main Authors | , , , , , , |
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Format | Journal Article |
Language | English |
Published |
18.11.2011
|
Online Access | Get full text |
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Summary: | Two similar synthetic pathways using the ligand
N
,
N
-diisobutylisonicotinamide (L) with anhydrous CoX
2
salts (being X = Cl
−
, Br
−
) led to different species: a one-dimensional system, [CoLCl
2
]
n
,
1
, and an ionic product [Co(L)
2
(H
2
O)
4
][CoLBr
3
]
2
·2H
2
O,
2
, respectively. Compound
1
is a polymer in which ligand L coordinates to tetrahedral Co
II
ions in a bidentate bridging fashion using the pyridine nitrogen and carbonyl oxygen atoms. Compound
2
consists of one octahedral cationic [Co(L)
2
(H
2
O)
4
]
2+
entity and two tetrahedral anionic [CoLBr
3
]
−
units. In this system, the ligand molecules coordinate only through the pyridine nitrogen atoms. The magnetic properties of
1
and
2
were investigated in the temperature range of 2.0 to 300.0 K and correlations between both (due to the existence of similar features) examined. The study of the magnetic properties of
1
was carried out by considering each Co
II
ion as a perfectly isolated system, hence,
J
= 0, but taking into account a significant zero-field splitting contribution due to distortions on the tetrahedral environment of the cobalt atoms. The fit of the magnetic susceptibility data together with reduced magnetization
vs H
/
T
measurements provided similar parameters (|
D
| = 10.8 cm
−1
,
g
= 1.92,
g
|
= 2.92 for the former and |
D
| = 11.04 cm
−1
and
g
= 2.05 for the latter, respectively). On the other hand, the magnetic response of compound
2
has been analyzed using a model which considers the presence of two tetrahedral and one octahedral Co(
ii
) ions (Co
Td
and Co
Oh
). The study was carried out in two separated blocks, above and below 80 K, where only the most significant effects at each interval of temperature were considered. As a result, the analysis of the magnetic data shows weak antiferromagnetic interactions between the Co
Oh
and the two Co
Td
ions (
J
= −0.41 cm
−1
) in
2
. The best fit parameters were
g
Co
Td
= 2.89,
g
Co
Oh
= 3.50, |
D
Co
Td
| = 10.62 cm
−1
, |
E
Co
Td
| = 2.95 cm
−1
, Δ = 240.9 cm
−1
and
J
L-S
= −107.1 cm
−1
, from where
λ
was calculated with a final value of −144.8 cm
−1
(
J
L-S
=
Aκλ
). The approximations performed to obtain these values provide reasonable results in agreement with compound
1
and also to other systems in the literature.
Structural and magnetic properties of two new Co(
ii
) compounds containing
N
,
N
-diisobutylisonicotinamide as the coordinating ligand. |
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Bibliography: | For ESI and crystallographic data in CIF or other electronic format see DOI Electronic supplementary information (ESI) available: CCDC reference numbers 10.1039/c1dt10991j 808174-808175 |
ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c1dt10991j |