Self-assembly of Ligands Designed for the Building of a New Type of [2 × 2] Metallic Grid. Anion Encapsulation and Diffusion NMR Spectroscopy
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- 作者：Blanca R. Manzano ; Fé ; lix A. Jaló ; n ; Isabel M. Ortiz ; M. Laura Soriano ; Felipe Gó ; mez de la Torre ; José ; Elguero ; Miguel A. Maestro ; Kurt Mereiter ; Tim D. W. Claridge
- 刊名：Inorganic Chemistry
- 出版年：2008
- 出版时间：January 21, 2008
- 年：2008
- 卷：47
- 期：2
- 页码：413 - 428
- 全文大小：707K
- 年卷期：v.47,no.2(January 21, 2008)
- ISSN：1520-510X
文摘
The ligands 4,6-bis(pyrazol-1-yl)pyrimidine (bpzpm), 4,6-bis(3,5-dimethylpyrazol-1-yl)pyrimidine (bpz*pm), 4,6-bis(4-methylpyrazol-1-yl)pyrimidine (Mebpzpm), and 3,6-bis(3,5-dimethylpyrazol-1-yl)pyridazine (ppdMe) were synthesizedand were made to react with Cu(I) centers in the presence of different counteranions. Different [2 × 2] metallicgrids were obtained. With ligands bpzpm, bpz*pm, and Mebpzpm, a new type of grid was obtained where thefacing ligands were divergent and two counteranions (BF4- or PF6-) were hosted in the resulting cavities andexhibit C-H···F and anion···
fchars/pi.gif" BORDER=0 > interactions in the solid state. The presence of methyl groups on the pyrazolyl ringsinduced several distortions in the structure. In complexes with the ligand ppdMe, there were found two groups ofparallel ligands in the grid, and the cavities generated were smaller. The counteranions were situated outside thegrid, and the facing ligands exhibited aromatic fchars/pi.gif" BORDER=0 >-fchars/pi.gif" BORDER=0 > stacking interactions. Anion-fchars/pi.gif" BORDER=0 > interactions involving the pyridazinering were found. The behavior in solution of the new derivatives with a special emphasis on the cation-anioninteractions was studied by UV-vis and NMR spectroscopy. Diffusion NMR experiments performed for somecomplexes allowed us to conclude that weak cation-anion interactions exist in solution, with the counteranionsundergoing fast exchange on the diffusion time scale between the free and ion-paired states.
fchars/pi.gif" BORDER=0 > interactions in the solid state. The presence of methyl groups on the pyrazolyl ringsinduced several distortions in the structure. In complexes with the ligand ppdMe, there were found two groups ofparallel ligands in the grid, and the cavities generated were smaller. The counteranions were situated outside thegrid, and the facing ligands exhibited aromatic fchars/pi.gif" BORDER=0 >-fchars/pi.gif" BORDER=0 > stacking interactions. Anion-fchars/pi.gif" BORDER=0 > interactions involving the pyridazinering were found. The behavior in solution of the new derivatives with a special emphasis on the cation-anioninteractions was studied by UV-vis and NMR spectroscopy. Diffusion NMR experiments performed for somecomplexes allowed us to conclude that weak cation-anion interactions exist in solution, with the counteranionsundergoing fast exchange on the diffusion time scale between the free and ion-paired states.