Framework control by a metalloligand having multicoordination ability: New synthetic approach for crystal structures and magnetic properties

Shin Ichiro Noro, Hitoshi Miyasaka, Susumu Kitagawa, Tatsuo Wada, Takashi Okubo, Masahiro Yamashita, Tadaoki Mitani

Research output: Contribution to journalArticlepeer-review

138 Citations (Scopus)

Abstract

By utilizing the novel metalloligand LCu, [Cu(2,4-pydca) 2]2- (2,4-pydca2- = pyridine-2,4-dicarboxylate) , which possesses two kinds of coordination groups, selective bond formation with the series of the first-period transition metal ions (MnII, FeII, CoII, CuII, and ZnII) has been accomplished. Depending on the coordination mode of 4-carboxylate with Co II, CuII, and ZnII ions, LCu forms a one-dimensional (1-D) assembly with a repeating motif of [-M-O 2C-(py)N-Cu-N(Py)-CO2-]: {[ZnLCu(H 2O)3(DMF)]·DMF}n (2), [ZnL Cu(H2O)2(MeOH)2]n (3), and {[MLCu(H2O)4]·2H2O} n (M = Co (4), Cu (5), Zn (6)). The use of a terminal ligand of 2,2′-bipyridine (2,2′-bpy), in addition to the CuII ion, gives a zigzag 1-D assembly with the similar repeating unit as 4-6: {[Cu(2,2′-bpy)LCu]-3H2O}n (9). On the other hand, for MnII and FeII ions, LCu shows a 2-carboxylate bridging mode to form an another 1-D assembly with a repeating motif of [-M-O-C-O-Cu-O-C-O-]: [MLCu(H2O) 4]n (M = Mn (7), Fe (8)). This selectivity is related to the strength of Lewis basicity and the electrostatic effect of LCu and the Irving-Williams order on the present metal ions. According to their bridging modes, a variety of magnetic properties are obtained: 4,5, and 9, which have the 4-carboxypyridinate bridge between magnetic centers, have weak antiferromagnetic interaction, whereas 7 and 8 with the carboxylate bridge between magnetic centers reveal 1-D ferromagnetic behavior (Cu II-MII; MII = MnII, J/kB = 0.69 K for 7; MII = FeII, J/kB = 0.71 K for 8).

Original languageEnglish
Pages (from-to)133-146
Number of pages14
JournalInorganic chemistry
Volume44
Issue number1
DOIs
Publication statusPublished - 2005 Jan 10
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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