Thyminato-bridged cyclic tetranuclear rhodium(III) complexes containing a sodium, calcium or lanthanoid ion as a template metal core

Mika Sakate, Ayana Kashima, Haruka Hosoda, Yukinari Sunatsuki, Hiromi Ota, Akira Fuyuhiro, Takayoshi Suzuki

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)


Reactions of [(CpRh)2(μ-OH)3]OH (Cp = η5-C5Me5) and thymine (=H2thym) in methanol in the presence or absence of a certain metal salt were examined. From the reaction mixture without any template metal salt, a dinuclear hydroxido-bridged complex bearing monodentate monodeprotonated thyminato ligands, [{CpRh(Hthym-κN1)}2(μ-OH)2], was isolated after recrystallization from water. In the presence of a metal salt MXn{=NaPF6, NaBF4, NaNO3, Ca(NO3)2, Ca(ClO4)2, La(NO3)3, Eu(NO3)3, Dy(NO3)3and Er(NO3)3} were deposited orange crystals (1P, 1B, 1N, 2N, 2C, 3N, 4N, 5N and 6N, respectively) which consist of a thyminato(2-)-bridged tetranuclear CpRh complex incorporating a Mn+cation, [(CpRh)4(μ-thym)4M]n+. All complexes were characterized by the single-crystal X-ray diffraction method, which revealed that homochiral aggregations of four RhIIIcenters were achieved to give metallacalix[4]arene-type clusters. It was also observed that the bridging modes of thym2−ligands were dependent on the template metal ion. In the Na+-incorporated clusters (1X, X = P, B or N) a thym2−ligand bridged two RhIIIand the third Na+ions with a μ3-1κN1:2κ2N3,O2:3κO2mode, while in the Ln3+analogs (Ln = La, Eu, Dy or Er: 3N–6N) thym2−exhibited a different bridging mode, μ3-1κN1:2κ2N3,O4:3κO2. In the cases of Ca2+-incorporated clusters, the bridging mode is further dependent on the associated anion; only the μ3-1κN1:2κ2N3,O2:3κO2-type cluster was obtained in the NO3salt (2N), but the ClO4salt (2C) afforded both types of the bridging clusters piled up alternatively in the crystals. The tetranuclear structures with a template metal cation, [(CpRh)4(μ-thym)4M]n+, are maintained in solution. The magnetic behaviors of the Dy3+- and Er3+-incorporated complexes (5N and 6N) are also reported.

Original languageEnglish
Pages (from-to)205-213
Number of pages9
JournalInorganica Chimica Acta
Publication statusPublished - 2016


  • Bridging isomers
  • Crystal structure
  • Heterometallic complexes
  • Metallacalix[n]arene
  • Template synthesis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


Dive into the research topics of 'Thyminato-bridged cyclic tetranuclear rhodium(III) complexes containing a sodium, calcium or lanthanoid ion as a template metal core'. Together they form a unique fingerprint.

Cite this