A thermally activated delayed fluorescence (TADF) tetrametallic Cu(I) metallacycle A behaves as a conformationally adaptive preorganized precursor to afford, through straightforward and rational coordination-driven supramolecular processes, a variety of room-temperature solid-state luminescent polymetallic assemblies. Reacting various cyano-based building blocks with A, a homometallic Cu(I) 1D-helical coordination polymer C and CuM discrete circular heterobimetallic assemblies D (M = Ni, Pd, Pt) are obtained. Their luminescence behaviors are studied, revealing notably the crucial impact of the spin-orbit coupling offered by the central M metal center on the photophysical properties of the heterobimetallic D derivatives.
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