Rational Design of a Phosphorus-Centered Disbiradical.

Phosphorus-centered disbiradicals, in which the radical sites exist as individual spin doublets with weak spin-spin interaction have not been known so far. Starting from monoradicals of the type [⋅P(µ-NTer)2 P-R], we have now succeeded in linking two such monoradical phosphorus centers by appropriate choice of a linker. To this end, biradical [⋅P(µ-NTer)2 P⋅] (1) was treated with 1,6-dibromohexane, affording the brominated species {Br[P(µ-NTer)]2 }2 C6 H12 (3). Subsequent reduction with KC8 led to the formation of the disbiradical {⋅[P(µ-NTer)]2 }2 C6 H12 (4) featuring a large distance between the radical phosphorus sites in the solid state and formally the highest biradical character observed in a P-centered biradical so far, approaching 100 %. EPR spectroscopy revealed a three-line signal in solution with a considerably larger exchange interaction than would be expected from the molecular structure of the single crystal. Quantum chemical calculations revealed a highly dynamic conformational space; thus, the two radical sites can approach each other with a much smaller distance in solution. Further reduction of 4 resulted in the formation of a potassium salt featuring the first structurally characterized P-centered distonic radical anion (5- ). Moreover, 4 could be used in small molecule activation.

Reversible Optical Switching of Polyoxovanadates and Their Communication via Photoexcited States.

The 2-bit Lindqvist-type polyoxometalate (POM) [V6O13((OCH2)3CCH2N3)2]2- with a diamagnetic {V6O19} core and azide termini shows six fully oxidized VV centers in solution as well as the solid state, according to 51V NMR spectroscopy. Under UV irradiation, it exhibits reversible switching between its ground S0 state and the energetically higher lying states in acetonitrile and water solutions. TD-DFT calculations demonstrate that this process is mainly initialized by excitation from the S0 to S9 state. Pulse radiolysis transient absorption spectroscopy experiments with a solvated electron point out photochemically induced charge disproportionation of VV into VIV and electron communication between the POM molecules via their excited states. The existence of this unique POM-to-POM electron communication is also indicated by X-ray photoelectron spectroscopy (XPS) studies on gold-metalized silicon wafers (Au//SiO2//Si) under ambient conditions. The amount of reduced vanadium centers in the "confined" environment increases substantially after beam irradiation with soft X-rays compared to non-irradiated samples. The excited state of one POM anion seems to give rise to subsequent electron transfer from another POM anion. However, this reaction is prohibited as soon as the relaxed T1 state of the POM is reached.