TY - JOUR
T1 - Thyminato-bridged cyclic tetranuclear rhodium(III) complexes containing a sodium, calcium or lanthanoid ion as a template metal core
AU - Sakate, Mika
AU - Kashima, Ayana
AU - Hosoda, Haruka
AU - Sunatsuki, Yukinari
AU - Ota, Hiromi
AU - Fuyuhiro, Akira
AU - Suzuki, Takayoshi
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research No. 25410070 from the Ministry of Education, Culture, Sports, Science, and Technology , Japan.
Publisher Copyright:
© 2016 Elsevier B.V.
PY - 2016
Y1 - 2016
N2 - Reactions of [(Cp∗Rh)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, [{Cp∗Rh(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 Cp∗Rh complex incorporating a Mn+cation, [(Cp∗Rh)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 NO3−salt (2N), but the ClO4−salt (2C) afforded both types of the bridging clusters piled up alternatively in the crystals. The tetranuclear structures with a template metal cation, [(Cp∗Rh)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.
AB - Reactions of [(Cp∗Rh)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, [{Cp∗Rh(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 Cp∗Rh complex incorporating a Mn+cation, [(Cp∗Rh)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 NO3−salt (2N), but the ClO4−salt (2C) afforded both types of the bridging clusters piled up alternatively in the crystals. The tetranuclear structures with a template metal cation, [(Cp∗Rh)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.
KW - Bridging isomers
KW - Crystal structure
KW - Heterometallic complexes
KW - Metallacalix[n]arene
KW - Template synthesis
UR - http://www.scopus.com/inward/record.url?scp=84955607180&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84955607180&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2016.01.023
DO - 10.1016/j.ica.2016.01.023
M3 - Article
AN - SCOPUS:84955607180
SN - 0020-1693
VL - 452
SP - 205
EP - 213
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -