Journal
DALTON TRANSACTIONS
Volume 50, Issue 41, Pages 14602-14610Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1dt02075g
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Funding
- Deutsche Forschungsgemeinschaft (DFG) [AP242/2-1, AP242/9-1]
- Fraunhofer Internal Programs [Attract 097-602175]
- DFG under Germany's Excellence Strategy -EXC-2033 [390677874]
- Deutsche Bundesstiftung Umwelt
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The study reports the synthesis of an asymmetric hexa-amine cryptand analogue by selectively exchanging three of the secondary amines of one binding site with sulphur atoms, allowing for the formation of stable dinuclear complexes of metals with different oxidation numbers.
Bis-tren (tren = tris(2-aminoethyl)amine) azacryptands were previously studied profoundly for the coordination of two +ii metals and subsequent binding of substrates within their cavity. Likewise, cryptates including metals in different oxidations states were reported with the rather unstable hexa-imine analogues but also revealed only little stability. In this work, we report the synthesis of an asymmetric hexa-amine cryptand analogue by selectively exchanging three of the secondary amines of one binding site with sulphur atoms. We show that the presence of two distinct binding sites allows for the selective formation of stable dinuclear complexes of metals with different oxidation numbers and present the formation of distinct (CuCoII)-Co-I, (CuNiII)-Ni-I and (CuCuIII)-Cu-I cryptates.
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