@misc{oai:ir.soken.ac.jp:00000312,
 author = {森下, 泰全 and モリシタ, ヒロマサ and MORISHITA, Hiromasa},
 month = {2016-02-17, 2016-02-17},
 note = {The metal-assisted assembly of cyclic molecular arrays plays an integral part in the development of inclusion chemistry as well as "engineering up" molecular architectures.  The creation of a new class of artificial chiral supramolecular species via spontaneous self-assembly has been one key to further development of this rapidly expanding field.  However, only a few examples of chiral molecular squares have been reported.  In particular, synthetic approach using achiral ligands is very rare.
  They describe a one-pot, high-yield synthesis of a novel cyclic tetranuclear ZnII complex (3-1) with 3, 6-di-2-pyridyl-1, 2, 4, 5-tetrazine (DPTZ), which was spontaneously resolved as chiral crystals (scheme 1).  The X-ray crystal structure and the solution behaviors of this complex (2-1) have been investigated in this work.  Interestingly, the individual single crystal was found to consist of one enantiomer only.  This is the first example of a quantitative formation of a spontaneously resolved cyclic product based on self assembly of metal ions and achiral ligands.  In addition, it is noteworthy that this is the first example of the chiral cyclic tetranuclear species that was constructed by kinetically labile ZnII complexes.  These results will provide a new tool for creating chiral supramolecular architectures using inherently chiral metal ions and achiral ligands.  Solvent effect on the structure of complex (2-1) and optical resolution of (2-1) were investigated using NMR, mass, and circular dichroism spectrometries.
  They found that the ligand DPTZ itself reacted with CuII and PbII ions, probably because these metals are stronger Lewis acids than ZnII ions.  Then they synthesized a more robust ligand, 2, 5-di-2-pyridyl-pyrazine (DPPZ), which was expected to form more stable metal complexes.
  They have prepared two types of one-dimensional polymers AgI polymer complexes with DPPZ.  The kind of counter anions dramatically affected their polymeric structures.  When perchlorate anions are used as the counter anion (3-5), AgI ions were aligned in the zig-zag manner (Fig 1), whereas AgI ions were aligned linearly when nitrate ions were used (Fig 2).  Further, in the former case, the coordination geometry of AgI is distorted square planar, while the latter complex is in the distorted octahedral geometry.  The fine structures and chemical properties of these complexes will be reported.
  The X-ray analysis of the ZnII complex of DPPZ is now underway to compare with that of DPTZ., application/pdf, 総研大甲第489号},
 title = {Bisbidentate型架橋配位子を用いた集積型金属錯体の合成と構造 -自然分晶する不斉環状亜鉛四核錯体},
 year = {}
}