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Dynamic combinatorial chemistry is a novel aspect of supramolecular chemistry dealing with the generation of dynamic libraries resulting from all the possible combinations of fragments of the constituents (keys). The receptors (locks) favour the expression of the keys that bind best to it (thermodynamic selection) or that form fastest within it (kinetic selection). The already mentioned in situ rich chemistry of the organosulfur ligands makes this system suitable for developing supramolecular dynamic combinatorial aspects under solvothermal conditions.Moreover, these kinds of organosulphur ligands seem to be especially suitable to form metal¨Csulphur¨Corganic networks with promising electronic properties.The incorporation of thiolate-S as a single atom bridge between adjacent transition metal sites could allow higher spin density delocalization towards the bridging atom and contribute to strong super-exchange interactions when the selected metal orbital energies are better matched for the sulphur atom. In principle, this beneficial feature is highly desirable in terms of magnetic, conductive and luminescent properties of the resulting materials.
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