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One-dimensional manganese coordination polymers composed of polynuclear cluster blocks and polypyridyl linkers: structures and properties

One-dimensional manganese coordination polymers composed of polynuclear cluster blocks and polypyridyl linkers: structures and properties
One-dimensional manganese coordination polymers composed of polynuclear cluster blocks and polypyridyl linkers: structures and properties
The synthesis, crystal structures and magnetic properties of five new manganese compounds are reported. These include a linear trinuclear cluster [Mn(II)(3)(O(2)CCHMe(2))(6)(dpa)(2)]center dot 2MeCN (1) (dpa = 2,2'-dipyridylamine), a tetranuclear cluster [Mn(II)(2)Mn(III)(2)O(2)(O(2)CCMe(3))(6)(bpy)(2)] (3) (bpy = 2,2'-bipyridine), and chain coordination polymers composed of cluster blocks such as Mn(3), Mn(3)O, and Mn(4)O(2) bridged by 2,2'-bipyrimidine (bpm) or hexamethylentetramine (hmta) ligands to give ([Mn(II)(2)Mn(III)(2)O(2)(O(2)CCMe(3))(6)(bpm)]center dot 2EtOH)(n) (2), [Mn(II)(2)Mn(III)(2)O(2)(O(2)CCHMe(2))(6)(bpm)(EtOH)(4)](n) (4), and (([Mn(II)(2)Mn(III)(2)O(2)(O(2)CCMe(3))(6)(hmta)(2)]center dot EtOH)(n) (5). The magnetic analysis of the compounds was achieved using a combination of vector coupling and full-matrix diagonalization methods. Susceptibility data for compound 1 was fitted using a vector coupling model to give g = 2.02(1) and 2J/k(B) = -5.38(2) K. To model the trimer chain, we used vector coupling for initial values of J(1) and then diagonalization techniques to estimate J(2) to give g = 1.98(1), 2J(1)/kB = -3.3(1) K and 2J(2)/k(B) = -1.0(1) K by approximating the system to a dimer of trimers. The analysis of 3 was made difficult by the mixture of polymorphs and the difficulties of a three-J model, while for 4 an analysis was not possible because of the size of the computation and the relative magnitudes of the three couplings. Compound 5 was modeled using the same techniques as 2 to give g = 1.99(1), 2J(1)/k(B) = +32.5(2) K, 2J(2)/k(B) = -16.8(1) K, and 2J(3)/k(B) = +0.4(1) K. The combination of techniques has worked well for compounds 2 and 5 and thus opens up a method of modeling complex chains.
0020-1669
11108-11119
Baca, Svetlana G.
bf5b0d5c-2e00-49c2-bfcc-05743a0d638d
Malaestean, Iurii L.
9051302d-c49e-4d14-8edc-20617a418369
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Adams, Harry
4379cc0a-3ba1-4b32-aa76-14f557e5c010
Ward, Michael D.
da487000-9f37-440b-a952-e09671f28e3b
Hauser, Jürg
eabd6bf7-344a-4bea-a073-79479dc06743
Neels, Antonia
a8d7f75b-c2c2-4d1f-bfb4-d538fd4c9073
Decurtins, Silvio
331985a5-2121-47e4-a4b2-2fd09f8cabfd
Baca, Svetlana G.
bf5b0d5c-2e00-49c2-bfcc-05743a0d638d
Malaestean, Iurii L.
9051302d-c49e-4d14-8edc-20617a418369
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Adams, Harry
4379cc0a-3ba1-4b32-aa76-14f557e5c010
Ward, Michael D.
da487000-9f37-440b-a952-e09671f28e3b
Hauser, Jürg
eabd6bf7-344a-4bea-a073-79479dc06743
Neels, Antonia
a8d7f75b-c2c2-4d1f-bfb4-d538fd4c9073
Decurtins, Silvio
331985a5-2121-47e4-a4b2-2fd09f8cabfd

Baca, Svetlana G., Malaestean, Iurii L., Keene, Tony D., Adams, Harry, Ward, Michael D., Hauser, Jürg, Neels, Antonia and Decurtins, Silvio (2008) One-dimensional manganese coordination polymers composed of polynuclear cluster blocks and polypyridyl linkers: structures and properties. Inorganic Chemistry, 47 (23), 11108-11119. (doi:10.1021/ic8014145).

Record type: Article

Abstract

The synthesis, crystal structures and magnetic properties of five new manganese compounds are reported. These include a linear trinuclear cluster [Mn(II)(3)(O(2)CCHMe(2))(6)(dpa)(2)]center dot 2MeCN (1) (dpa = 2,2'-dipyridylamine), a tetranuclear cluster [Mn(II)(2)Mn(III)(2)O(2)(O(2)CCMe(3))(6)(bpy)(2)] (3) (bpy = 2,2'-bipyridine), and chain coordination polymers composed of cluster blocks such as Mn(3), Mn(3)O, and Mn(4)O(2) bridged by 2,2'-bipyrimidine (bpm) or hexamethylentetramine (hmta) ligands to give ([Mn(II)(2)Mn(III)(2)O(2)(O(2)CCMe(3))(6)(bpm)]center dot 2EtOH)(n) (2), [Mn(II)(2)Mn(III)(2)O(2)(O(2)CCHMe(2))(6)(bpm)(EtOH)(4)](n) (4), and (([Mn(II)(2)Mn(III)(2)O(2)(O(2)CCMe(3))(6)(hmta)(2)]center dot EtOH)(n) (5). The magnetic analysis of the compounds was achieved using a combination of vector coupling and full-matrix diagonalization methods. Susceptibility data for compound 1 was fitted using a vector coupling model to give g = 2.02(1) and 2J/k(B) = -5.38(2) K. To model the trimer chain, we used vector coupling for initial values of J(1) and then diagonalization techniques to estimate J(2) to give g = 1.98(1), 2J(1)/kB = -3.3(1) K and 2J(2)/k(B) = -1.0(1) K by approximating the system to a dimer of trimers. The analysis of 3 was made difficult by the mixture of polymorphs and the difficulties of a three-J model, while for 4 an analysis was not possible because of the size of the computation and the relative magnitudes of the three couplings. Compound 5 was modeled using the same techniques as 2 to give g = 1.99(1), 2J(1)/k(B) = +32.5(2) K, 2J(2)/k(B) = -16.8(1) K, and 2J(3)/k(B) = +0.4(1) K. The combination of techniques has worked well for compounds 2 and 5 and thus opens up a method of modeling complex chains.

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More information

e-pub ahead of print date: 28 October 2008
Published date: 1 December 2008
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

Identifiers

Local EPrints ID: 350204
URI: https://eprints.soton.ac.uk/id/eprint/350204
ISSN: 0020-1669
PURE UUID: c207ba81-f6a3-4ace-906a-c6d124efd760
ORCID for Tony D. Keene: ORCID iD orcid.org/0000-0003-2297-4327

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Date deposited: 19 Mar 2013 16:45
Last modified: 12 Nov 2019 01:37

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