There remains considerable interest in developing methods for the targeted delivery of nitric oxide and other small molecule bioregulators such as carbon monoxide to physiological targets. One such strategy is to use a "caged" NO that is "uncaged" by excitation with light. Such photochemical methods convey certain key advantages such as the ability to control the timing, location and dosage of delivery, but also have some important disadvantages, such as the relatively poor penetration of the ultraviolet and visible wavelengths often necessary for the uncaging process. Presented here is an overview of ongoing studies in the author's laboratory exploring new photochemical NO precursors including those with nanomaterial antennas designed to enhance the effectiveness of these precursors with longer excitation wavelengths.