We have discovered five bismuth(III)-containing polyoxopalladates (POPs) which were fully characterized by solution and solid-state physicochemical techniques: the cube-shaped [BiPd₁₂O₃₂(AsPh)₈]^5- (BiPd₁₂AsL), [BiPd₁₂O₃₂(AsC₆H₄N₃)₈]^5- (BiPd₁₂AsL_N), and [BiPd₁₂O₃₂(AsC₆H₄COO)₈]^13- (BiPd₁₂AsL_C) as well as the star-shaped [BiPd₁₅O₄₀(PO)₁₀H₆]^11- (BiPd₁₅P) and [BiPd₁₅O₄₀(PPh)₁₀]^7- (BiPd₁₅PL), respectively. The organically modified capping groups phenylarsonate, p-azidophenylarsonate, and p-carboxyphenylarsonate were chosen as the azido (-N₃) and carboxyl (-COOH) groups open up opportunities to covalently conjugate (via click reaction, amide coupling, etc.) with targeting vectors. The synthesis of p-azidophenylarsonate is reported here for the first time. The effects of the Bi^III template and the organoarsonate vs -posphonate capping groups on the resulting POP shape (cube vs star) are discussed. The ²⁰⁹Bi NMR (I = 9/2) spectra of BiPd₁₂AsL, BiPd₁₂AsL_N, and BiPd₁₂AsL_C revealed narrow peaks (ν_1/2 ∼ 200 Hz) at 5470 ppm with a longitudinal relaxation time in the millisecond range (at 8.46 T). The absence of a quadrupolar relaxation contribution could be attributed to the allocation of Bi^III in the highly symmetrical cuboid POP host cage. Similar peaks were absent in the ²⁰⁹Bi-NMR spectra of the star-shaped POPs BiPd₁₅P and BiPd₁₅PL due to the less symmetric coordination environment around the central Bi^III ion. Further, ^205/206Bi-radiolabeled POPs have been synthesized by incorporating a ^205/206Bi^III ion in the center of the POP structures. Carrier-free ^205/206Bi radioisotopes (as surrogates of α-emitting ²¹³Bi) were incorporated into the POP host-cage for the preparation of ^205/206BiPd₁₂AsL, ^205/206BiPd₁₂AsL_N, ^205/206BiPd₁₂AsL_C, and ^205/206BiPd₁₅PL, respectively. The radiometal incorporation was complete (>99% radiochemical yield) in 10 min according to radio-thin-layer chromatography. The ^205/206BiPd₁₂AsL polyanion was purified by solid-phase extraction. The incubation in rat serum showed the formation of a ^205/206BiPd₁₂AsL-protein aggregate.

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