超分子体系中次层相互作用对59Co NMR谱的影响

用＾５０Ｃｏ固体静态ＮＭＲ对〔Ｃｏ（ＣＮ６〕＾３－离子与质子化的大环聚胺阳离子形成的超分子络合物的次层相互作用进行研究，结果表明，氢键的形成对该超分子结构的稳定性起了重要的作用。与仅有静电作用存在的Ｋ３〔ＣｏＣＮ）６〕分子相比，＾５９Ｃｏ的三个化学位移张量的主值差值在超分子体系中明显增大。氢键作用的结果使〔Ｃｏ（ＣＮ６〕３－的对称性发生了改变，导致＾１Ｔ１ｇ三重简并态发生分裂。分裂的大小反映了相互

The Second Sphere Interaction in the Supramolecular Complexes Studied by 59Co Solid Static NMR

59Co solid static NMR has demontrated that the hydrogen bonding interaction plays an important role in the supramolecular complexes formed by the Co (CN)6]3- and protonated polyammonium macrocycles. The 59Co chemical shift spans Ω in the supramolecular complexes containing hydrogen boning interaction are considerably larger than that in K3Co(CN)6] which bears the electronic static interaction only. Hydrogen bonding interaction changes the symmetry, of Co(CN)6]3- in the supramolecules leading to the split of the triplex degenerate state 1T1g and the extent of the split reveals the extent of the hydrogen bonding. Accordingly, the changes of the aquation quantum yields in the supramolecules are alternatively rationalized.