| Autor: |
Pham CT; VNU University of Science, Vietnam National University , Hanoi, Department of Inorganic Chemistry , 19 Le Thanh Tong , Hanoi , Vietnam., Barnard I; Department of Chemistry and Polymer Science , University of Stellenbosch , P Bag X1, Matieland, Stellenbosch 7602 , South Africa., Nguyen HH; VNU University of Science, Vietnam National University , Hanoi, Department of Inorganic Chemistry , 19 Le Thanh Tong , Hanoi , Vietnam., Abram U; Freie Universität Berlin , Institute of Chemistry and Biochemistry , Fabeckstr. 34/36 , D-14195 Berlin , Germany., Koch KR; Department of Chemistry and Polymer Science , University of Stellenbosch , P Bag X1, Matieland, Stellenbosch 7602 , South Africa. |
| Abstrakt: |
One-pot reactions of the catechol-scaffolding aroylbis( N , N -diethylthiourea) H 2 L cat with mixtures of CoCl 2 and MCl (M + = Cs + , Rb + , K + , Tl + , or NH 4 + ) or with a Co(NO 3 ) 2 /TlNO 3 mixture lead to the self-assembly of a series of cationic Co(III) metallacryptates of the general formula [M ⊂ {Co 2 (L cat ) 3 }] + (M + = Cs + , Rb + , K + , Tl + , or NH 4 + ). Crystalline PF 6 - salts were obtained after workup with ( n -Bu 4 N)(PF 6 ), and the single-crystal structures of all five metallacryptates have been determined. Depending on the nature of the guest cations, the directional interactions between guest cations and the metallacryptand {Co 2 (L cat ) 3 } are either weak coordination contacts or hydrogen bonds. The bonding mode and the size of the guest ions slightly influence the molecular skeleton of the host molecule. These small structural variations also exist in solution and could be detected by means of 59 Co NMR spectroscopy, which is shown to be a unique tool for an easy characterization of such compounds. 59 Co NMR chemical shifts are extraordinarily sensitive to the guest cation in the metallacryptates, and time-arrayed 59 Co NMR experiments show that cation-exchange processes in biphasic organic/aqueous systems can be studied in detail. This leads to insights into the relative rates of cation exchange, as well as the relative conditional distribution coefficients of such Co(III) metallacryptates between the aqueous and organic phases. Thus, the extent and the relative rate of the NH 4 + ion exchange in [NH 4 ⊂ {Co 2 (L cat ) 3 }](PF 6 ) by Cs + and K + ions across the organic/aqueous phase boundary at room temperature have been studied by in situ 59 Co NMR experiments. Preliminary 59 Co NMR experiments show that the K + ion in [K ⊂ {Co 2 (L cat ) 3 }](PF 6 ) can be removed by its competitive complexation with the highly potassium-selective [2.2.2]cryptand, to give a transient 59 Co NMR signal of the relatively unstable "empty" {Co 2 (L cat ) 3 } complex, which slowly decomposes in solution. |
