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Variations in topology and magnetic properties of hepta- and octacyanometallates of molybdenum with manganese(ii)Electronic supplementary information (ESI) available: Magnetic data for compounds 1-4. CCDC 973467-973470. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3dt53485e
Treatment of [Mn(dpop)(H 2 O) 2 ]Cl 2 (dpop = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene) with K 4 [Mo(CN) 7 ]·2H 2 O under varied synthetic conditions afforded four different compounds: {[Mn(dpop)] 4 [(dpop)Mn(H 2 O)] 2 [Mo III (CN) 7 ] 3 ·27H 2 O} n ( 1 ),...
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| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
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| Summary: | Treatment of [Mn(dpop)(H
2
O)
2
]Cl
2
(dpop = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene) with K
4
[Mo(CN)
7
]·2H
2
O under varied synthetic conditions afforded four different compounds: {[Mn(dpop)]
4
[(dpop)Mn(H
2
O)]
2
[Mo
III
(CN)
7
]
3
·27H
2
O}
n
(
1
), {[(dpop)Mn(H
2
O)][Mo
III
(CN)
7
][Mn(dpop)]
3
[Mo
IV
(CN)
8
]·29H
2
O}
n
(
2
), {[(dpop)Mn(H
2
O)]
2
[Mo
IV
(CN)
8
]
2
[Mn(dpop)]
4
[Mo
III
(CN)
7
]·12H
2
O}
n
(
3
), and [(dpop)Mn(H
2
O)]
2
[Mo
IV
(CN)
8
]·9H
2
O (
4
). Compound
1
contains only [Mo
III
(CN)
7
]
4−
anions and exhibits a corrugated two-dimensional layered architecture. The structure of
2
with a 1 : 1 ratio of Mo
III
: Mo
IV
is best described as a ladder-like chain composed of [Mo
III
(CN)
7
]
4−
-based pentanuclear [Mo
III
Mn
II
4
] fragments which are further linked by
in situ
produced [Mo
IV
(CN)
8
]
4−
anions. In the case of
3
, [Mn
8
Mo
8
] rings containing bent [Mo
III
Mn
II
2
] fragments are extended into a two-dimensional layer with the ratio of [Mo(CN)
7
]
4−
: [Mo(CN)
8
]
4−
being 1 : 2. Compound
4
exhibits a bent trinuclear structure in which two CN
−
groups of [Mo(CN)
8
]
4−
function as μ
2
-bridges to [Mn(dpop)(H
2
O)]
2+
fragments. Magnetic studies suggest significant antiferromagnetic coupling interactions occur between Mo(
iii
) and Mn(
ii
) ions while, not surprisingly, interactions between the Mn(
ii
) ions through diamagnetic [Mo
IV
(CN)
8
]
4−
anions are negligible. Compound
1
exhibits ferrimagnetic ordering below 3.0 K whereas
2
shows the signature of single molecule magnet behavior with slow relaxation of the magnetization and an effective energy barrier (
U
eff
) of 8.1 K.
Treatment of [Mn(dpop)(H
2
O)
2
]Cl
2
with K
4
[Mo(CN)
7
]·2H
2
O under varied synthetic conditions afforded four different compounds that exhibit a diversity of structures and magnetic properties. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c3dt53485e |