波谱学杂志 ›› 2004, Vol. 21 ›› Issue (1): 1-15.

• 研究论文 •    下一篇

钴超分子络合物中的氢键相互作用——59Co核磁共振研究及分子模拟

周平1*, 欧阳植勋2   

  1. 1.聚合物分子工程教育部重点实验室,复旦大学,高分子科学系,上海 200433;
    2.香港中文大学化学系,香港
  • 收稿日期:2003-08-18 修回日期:2002-09-15 出版日期:2004-03-05 发布日期:2004-03-05
  • 基金资助:

    The project was supported by NSFC (No. 20274009, 29974004).

HYDROGEN BONDING INTERACTION IN COBALTIC SUPRAMOLECULAR COMPLEXES—STUDIED 59Co NMR AND MOLECULAR MODELLING

 ZHOU Ping1*, AU-YANG S C F2   

  1. 1.The Key Laboratory of Molecular Engineering of Polymers, Ministry of Educati on. Macromolecular Science Department, Fudan University, Shanghai 200433, China;
    2.Department of Chemistry, The Chinese University of Hong Kong, Hong Kong, China
  • Received:2003-08-18 Revised:2002-09-15 Online:2004-03-05 Published:2004-03-05
  • Supported by:

    The project was supported by NSFC (No. 20274009, 29974004).

摘要:

钴超分子络合物[12]aneN4[Co(CN)6], [18]aneN6[Co(CN)6], [24] aneN8[Co(CN)6], [16] aneN4[Co(CN)6], [24] aneN6[Co(CN)6]以及[32] aneN8[Co(CN)6]中, 氢键相互作用的程度与它们在水溶液中的构象密切相关, 从而引起59Co的化学位移向高场移动, 并且其四极矩耦合作用也随构象发生了变化. 实验证明, 络合物中的氢键越强, 化学位移越向高场移动, 四极矩耦合作用也越大. 另一方面, 尺寸大的超分子具有较长的分子转动相关时间,  也导致59Co具有较短的纵向弛豫时间. 简而言之, 59Co核磁共振不仅在小分子甚至在超分子络合物中都可以用作理想的探针研究分子的次层或弱相互作用.

关键词: 59Co NMR, 氢键相互作用, 超分子络合物

Abstract:

The hydrogen bonding interactions in a series of cobaltic supramolecular complexes [12] aneN4[Co(CN)6], [18] aneN6[Co(CN)6], [24]aneN8[Co(CN)6], [16] aneN4[Co(CN)6], [24] aneN6[Co(CN)6] and [32] aneN8[Co(CN)6] were studies and found to be closely related to the molecular conformations in the aqueous solution. Such interactions caused the 59Co chemical shifts to move towards upfield, and the quadrupolar interaction to change as well. It was observed in this study that stronger hydrogen bonding resulted in larger upfield shift of the 59Co chemical shifts and higher quadrupolar interaction in the cobaltic supramolecular complexes. On the other hand, larger supramolecular sizes resulted in longer molecular rotational correlation time τand shorter 59Co longitudinal relaxation time (T1).  In summary, 59Co NMR proves to be an ideal probe to investigate the second sphere or weak interaction in the cobaltic supramolecular complexes in addition to the small molecules.

Key words: 59Co NMR, hydrogen bonding interaction, supramolecular complex