A new zinc phthalocyanine-zinc porphyrin dyad (ZnPc-ZnP) fused through a pyrazine ring has been synthesized as a receptor for imidazole-substituted C (CIm) electron acceptor. Self-assembly via metal-ligand axial coordination and the pertinent association constants in solution were determined by H-NMR, UV-Vis and fluorescence titration experiments at room temperature. The designed host was able to bind up to two CIm electron acceptor guest molecules to yield CIm:ZnPc-ZnP:ImC donor-acceptor supramolecular complex. The spectral data showed that the two binding sites behave independently with binding constants similar in magnitude. Steady-state fluorescence studies were indicative of an efficient singlet-singlet energy transfer from zinc porphyrin to zinc phthalocyanine within the fused dyad. Accordingly, the transient absorption studies covering a wide timescale of femto-to-milli seconds revealed ultrafast energy transfer from ZnP* to ZnPc (k ∼ 10 s) in the fused dyad. Further, a photo induced electron transfer was observed in the supramolecularly assembled CIm:ZnPc-ZnP:ImC donor-acceptor complex leading to charge separated states, which persisted for about 200 ns.

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http://dx.doi.org/10.1039/c8cp00382cDOI Listing

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