Yamanari Kazuaki, Fukuda Ito, Kawamoto Tatsuya, Kushi Yoshihiko, Fuyuhiro Akira, Kubota Naoko, Fukuo Tsuyoshi, Arakawa Ryuichi
Department of Chemistry, Graduate School of Science, Osaka University, 1-16 Machikaneyama-cho, Toyonaka, Osaka 560-0043, Japan, and Department of Applied Chemistry, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka 564-8680, Japan.
Inorg Chem. 1998 Oct 19;37(21):5611-5618. doi: 10.1021/ic9802146.
The cyclic multinuclear complexes Co(n)()(L-N,S,N')(n)()(tacn)(n)()()(+) (L = purine-6-thiones; tacn = 1,4,7-triazacyclononane) were synthesized through self-assembly of the mononuclear complex Co(HL-N,S)Cl(tacn) based on the multidentate bridging ability of purine-6-thione. Three kinds of purine-6-thione ligands were used: 9H-purine-6(1H)-thione (H(2)put), 2-amino-9H-purine-6(1H)-thione (H(2)aput), and 3,6-dihydro-6-thioxo-9H-purin-2(1H)-one (H(3)tpuo). The complexes Co(n)()(L-N,S,N')(n)()(tacn)(n)()()(+), n = 3 and 4 for put and n = 4 for aput and Htpuo, were characterized by NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and X-ray crystal structure analysis. ESI-MS proved to be a very powerful tool for determining the nuclearity (n value) unambiguously. X-ray crystal structure analyses of Co(4)(put)(4)(tacn)(4)(4).12H(2)O [triclinic, P&onemacr; (No. 2)] and [Co(4)(aput)(4)(tacn)(4)]Cl(4).16H(2)O [monoclinic, C2/c (No. 15)] reveal that all purinethione ligands act as tridentate ligands via S(6)/N(7) chelation and the N(9) bridge and both tetranuclear complexes adopt the cyclic S(4) structure which is stabilized by four intramolecular hydrogen bonds between N(3) and H-N(tacn). The trinuclear complex Co(3)(put)(3)(tacn)(3) having the C(1) structure was optically resolved. Stereochemistry for the cyclic molecular boxes containing chiral octahedral ions is developed.
通过基于嘌呤 - 6 - 硫酮的多齿桥联能力，由单核配合物[Co(HL - N,S)Cl(tacn)]⁺自组装合成了环状多核配合物[Coₙ(L - N,S,N')ₙ(tacn)ₙ]⁺（L = 嘌呤 - 6 - 硫酮；tacn = 1,4,7 - 三氮杂环壬烷）。使用了三种嘌呤 - 6 - 硫酮配体：9H - 嘌呤 - 6(1H) - 硫酮（H₂put）、2 - 氨基 - 9H - 嘌呤 - 6(1H) - 硫酮（H₂aput）和3,6 - 二氢 - 6 - 硫代 - 9H - 嘌呤 - 2(1H) - 酮（H₃tpuo）。配合物[Coₙ(L - N,S,N')ₙ(tacn)ₙ]⁺，对于put，n = 3和4，对于aput和Htpuo，n = 4，通过核磁共振光谱、电喷雾电离质谱（ESI - MS）和X射线晶体结构分析进行了表征。ESI - MS被证明是明确确定核数（n值）的非常强大的工具。Co₄(put)₄(tacn)₄₄·12H₂O[三斜晶系，P&onemacr;（编号2）]和[Co₄(aput)₄(tacn)₄]Cl₄·16H₂O[单斜晶系，C2/c（编号15）]的X射线晶体结构分析表明，所有嘌呤硫酮配体通过S(6)/N(7)螯合和N(9)桥作为三齿配体起作用，并且两种四核配合物都采用环状S₄结构，该结构通过N(3)与H - N(tacn)之间的四个分子内氢键得以稳定。具有C₁结构的三核配合物[Co₃(put)₃(tacn)₃]³⁺被拆分。发展了包含手性八面体离子的环状分子盒的立体化学。
