M+(12-crown-4) Supramolecular Cations (M+ = Na+, K+, Rb+, and NH4+) within Ni(2-thioxo-1,3-dithiole-4,5-dithiolate)2
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- 作者：Tomoyuki Akutagawa ; Tatsuo Hasegawa ; Takayoshi Nakamura ; Sadamu Takeda ; Tamotsu Inabe ; Ken-ichi Sugiura ; Yoshiteru Sakata ; and Allan E. Underhill
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：June 12, 2000
- 年：2000
- 卷：39
- 期：12
- 页码：2645 - 2651
- 全文大小：188K
- 年卷期：v.39,no.12(June 12, 2000)
- ISSN：1520-510X
文摘
Monovalent cations (M+ = Na+, K+, Rb+, and NH4+) and 12-crown-4 were assembled to new supramolecularcation (SC+) structures of the M+(12-crown-4)n (n = 1 and 2), which were incorporated into the electricallyconducting Ni(dmit)2 salts (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate). The Na+, K+, and Rb+ salts are isostructural with a stoichiometry of the M+(12-crown-4)2[Ni(dmit)2]4, while the NH4+ salt has a stoichiometry ofNH4+(12-crown-4)[Ni(dmit)2]3(CH3CN)2. The electrical conductivities of the Na+, K+, Rb+, and NH4+ salts atroom temperature are 7.87, 4.46, 0.78, and 0.14 S cm-1, respectively, with a semiconducting temperaturedependence. The SC+ structures of the Na+, K+, and Rb+ salts have an ion-capturing sandwich-type cavity ofM+(12-crown-4)2, in which the M+ ion is coordinated by eight oxygen atoms of the two 12-crown-4 molecules.On the other hand, the NH4+ ion is coordinated by four oxygen atoms of the 12-crown-4 molecule. Judging fromthe M+-O distances, thermal parameters of oxygen atoms, and vibration spectra, the thermal fluctuation of theNa+(12-crown-4)2 structure is larger than those of K+(12-crown-4)2 and Rb+(12-crown-4)2. The SC+ unit withthe larger alkali metal cation gave a stress to the Ni(dmit)2 column, and the SC+ structure changed the 
-overlap mode and electrically conducting behavior.
-overlap mode and electrically conducting behavior.