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Synthesis of Functionalized Aza-macrocycles and the Application of Their Metal Complexes in Binding Processes
Authors:Burkhard König  Mario Pelka  Michael Klein  Ina Dix  Peter G Jones  Johann Lex
Institution:(1) Institut für Organische Chemie und Institut für Anorganische und Analytische Chemie, Technischen Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany;(2) Institut für Anorganische und Analytische Chemie, Technischen Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany;(3) Institut für Organische Chemie, Universität zu Köln, Greinstraße 4, D-50939 Köln, Germany
Abstract:Although aza-macrocycles have beenthoroughly investigated ever since their discoverybecause of their interesting binding properties,recent applications of their metal complexes inmedical concepts or as binding sites for recognitionin water have increased the demand for efficientsyntheses of functionalized derivatives. We presenthere two approaches to functionalized aza-macrocycles:substituted cyclams have been obtained byheterogeneous hydrogenation of unsaturatedheterocycles, and with established coupling methodsfrom peptide chemistry the selective introduction offunctional groups and tethering of cyclens wasachieved. The ability of Lewis-acidic complexes ofsuch substituted aza-macrocycles to reversibly formdefined aggregates even in neutral aqueous solutionwas demonstrated with the synthesis of an electrondonor – electron acceptor dyad, which is capable ofundergoing a very efficient intramolecular photoinducedelectron transfer.
Keywords:aza-macrocycles  cyclen  cyclam  Lewis-acids  metal complexes  coordinative bonds
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