Two
trinuclear cyclometalated iridium(III)-based complexes of M-Ir-M
(M = Re, Ir) type were strategically designed with characteristically
different electron distributions based on the electronegativities
of Re and Ir. Photoinduced intramolecular electron transfer (PIIET)
is readily observed in these complexes with different lifetimes of
the radicals. The free amine ends of these symmetric complexes act
as the electron donor for PIIET. These ends, on the other hand, can
also act as centers for reducing gold (Au) salt (HAuCl4·3H2O) to generate Au atomistic nanoclusters (AuNCs)
protected and templated by the trinuclear complexes. Formation of
the AuNCs completely stops the PIIET and induces excited state intersystem
charge transfer (ESICT) from the surrounding complexes to the AuNC
core on exciting the system with radiation of the same wavelength.
The trinuclear cyclometalated complexes were synthesized by chelation
of the transition metal units, such as Re(CO)3Cl and Ir(ppy)2, to thiosemicarbazone (TSC) appended with cyclometalated
ligands of the precursor Ir(III) complex. Such a phenomenon of conversion
of PIIET in a trinuclear cyclometalated coordination complex completely
to ESICT on coupling to a noble metal nanocluster is unique and promising
for applications in energy devices.