Controlled switching of the spin state of transition metal ions, particularly of FeII and FeIII, is a prerequisite to achieve selectivity, efficiency, and catalysis in a number of metalloenzymes. Here we report on an iron(III) porphyrin with a photochromic axial ligand which, upon irradiation with two different wavelengths reversibly switches its spin state between low-spin (S = 1/2) and high-spin (S = 5/2) in solution (DMSO-acetone, 2:598). The switching efficiency is 76% at room temperature. The system is neither oxygen nor water sensitive, and no fatigue was observed after more than 1000 switching cycles. Concomitant with the spin-flip is a change in redox potential by ~60 mV. Besides serving as a simple model for the first step of the cytochrome P450 catalytic cycle, the spin switch can be used to switch the spin-lattice relaxation time T1 of the water protons by a factor of 15.

Chemists usually synthesize molecules using stochastic bond-forming collisions of the reactant molecules in solution. Nature follows a different strategy in biochemical synthesis. The majority of biochemical reactions are driven by machine-type protein complexes that bind and position the reactive molecules for selective transformations. Artificial "molecular assemblers" performing "mechanosynthesis" have been proposed as a new paradigm in chemistry and nanofabrication. Here we present a simple non-proteinogenic machine-type molecule which drives the endergonic condensation of vanadate to cyclic tetravanadate using light as the energy source. The system combines selective binding of the reactants, accurate positioning, and active release of the product. Hydrolysis of the product prevents inhibition of further cycles. Our prototypic system demonstrates the prerequisites that are needed to selectively drive an endergonic reaction using an external energy source.