Two-dimensional networks based on Mn4 complex linked by dicyanamide anion: From single-molecule magnet to classical magnet behavior

Hitoshi Miyasaka, Kazuya Nakata, Lollita Lecren, Claude Coulon, Yasuhiro Nakazawa, Tatsuya Fujisaki, Ken Ichi Sugiura, Masahiro Yamashita, Rodolphe Clérac

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249 Citations (Scopus)


Three two-dimensional (2D) network compounds based on Mn III/MnII tetranuclear single-molecule magnets (SMMs) connected by dicyanamide (dcn-) linkers have been synthesized: [Mn4(hmp)4(Hpdm)2-(dcn)2](CIO4) 2·2H2O·2MeCN (2), [Mn4(hmp) 4Br2(OMe)2(ccn)2]·0.5H 2O·2THF (3), [Mn4(hmp)6(dcn) 2](CIO4)2 (4), where Hhmp and H2pdm are 2-hydroxymethylpyridine and pyridine-2,6-dimethanol, respectively. The [Mn4]/dcn- system appears very versatile, but enables its chemistry to be rationalized by a fine-tune of the synthetic conditions. The double cuboidal [Mn4] unit is preserved in the whole family of compounds, despite strong modifications of its MnII coordination sphere. The chemical control of the coordination number of dcn- on the MnII sites has been the key to obtain the following series of compounds: a discrete cluster, [Mn4(hmp)6(NO 3)2(dcn)2]·2MeCN (1), 2D networks (2, 3, and 4), and the previously reported 3D compound, [Mn4(hmp) 43-OH)2][MnII(dcn) 6]·2MeCN·THF. Direct current magnetic measurements show that both Mn2+-Mn3+ and Mn3+-Mn3+ intra-[Mn4] magnetic interactions are ferromagnetic leading to an ST = 9 ground state for the [Mn4] unit. Despite the very similar 2D lattices in 2-4, the two kinds of orientation of the [Mn4] unit (i.e., angle variations between the two easy axes) lead to different magnetic properties ranging from SMM behavior for 2 and 1 to a long-range canted antiferromagnetic order for 4. Compound 3 is more complicated as the magnetic measurements strongly suggest the presence of a canted antiferromagnetic order below 2.1 K, although the magnetization slow relaxation is simultaneously observed. Heat capacity measurements confirm the long-range magnetic order in 4, while in 3, the critical behavior is frozen by the slow relaxation of the anisotropic [Mn4] units.

Original languageEnglish
Pages (from-to)3770-3783
Number of pages14
JournalJournal of the American Chemical Society
Issue number11
Publication statusPublished - 2006 Mar 22
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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