Luminescent Gold Surfaces for Sensing and Imaging: Patterning of Transition Metal Probes

Luminescent transition metal complexes are introduced for the microcontact printing of optoelectronic devices. Novel ruthenium(II), RubpySS, osmium(II), OsbpySS, and cyclometalated iridium(111), IrbpySS, bipyridyl complexes with long spacers between the surface-active groups and the metal were developed to reduce the distance-dependent, nonradiative quenching pathways by the gold surface. Indeed, surface-immobilized RubpySS and IrbpySS display strong red and green luminescence, respectively, on planar gold surfaces with luminescence lifetimes of 210 ns (RubpySS.Au) and 130 and 12 ns (83%, 17%) (IrbpySS-Au). The modified surfaces show enhancement of their luminescence lifetime in comparison with solutions of the respective metal complexes, supporting the strong luminescence signal observed and introducing them as ideal inorganic probes for imaging applications. Through the technique of microcontact printing, complexes were assembled in patterns defined by the stamp. Images of the red and green patterns rendered by the RubpySS-Au and IrbpySS.Au monolayers were revealed by luminescence microscopy studies. The potential of the luminescent surfaces to respond to biomolecular recognition events is demonstrated by addition of the dominant blood-pool protein, bovine serum albumin (BSA). Upon treatment of the surface with a BSA solution, the RubpySS-Au and IrbpySS-Au monolayers display a large luminescence signal increase, which can be quantified by time-resolved measurements. The interaction of BSA was also demonstrated by surface plasmon resonance (SPR) studies of the surfaces and in solution by circular dichroism spectroscopy (CD). Overall, the assembly of arrays of designed coordination complexes using a simple and direct mu-contact printing method is demonstrated in this study and represents a general route toward the manufacture of micropatterned optoelectronic devices designed for sensing applications.