Molecular Spin State Switching and Photochromism in the Red and Near Infrared with Ni(II) Chlorin and Ni(II) Bacteriochlorin

Molecules or ions are either paramagnetic (unpaired electrons) or diamagnetic (all electrons are paired). Switching between the two states under ambient conditions was considered a typical solid state phenomenon and has been termed spin crossover. The first single-molecule spin state switches operated with light in solution were developed a decade ago and offer a number of technical applications that are not accessible to solid state systems. Magnetic switching in biological environments, however, requires water solubility, and for in vivo applications, switching wavelengths within the bio-optical window (650-950 nm) are needed. We now present molecular spin state switches that are water-soluble and switchable in the far-red and near-infrared region. At the same time, they are photochromic compounds with excellent photophysical properties. trans-cis isomerization is induced with 505 nm radiation, and cis-trans conversion with 620 or 720 nm radiation. The metastable cis isomers are stable at room temperature for at least several weeks. The detailed mechanism of this surprising and unprecedented long wavelength photoisomerization of azobenzenes is still under investigation.