A new synthetic route to monoclinic bismuth vanadate using a concept adapted from a nonaqueous synthesis strategy for nanostructured organic–inorganic hybrid materials and metal oxides, introduced recently as twin polymerization, is reported. Microwave‐assisted synthesis starting from bismuth(III) tert‐butoxide and vanadium(V) oxytri(tert‐butoxide) in the presence of 2‐methoxybenzyl alcohol, 2,4‐dimethoxybenzyl alcohol, and 2‐(2‐thienyl)iso‐propyl alcohol gave hybrid materials, which were characterized by solid‐state 13C NMR spectroscopy, CH analysis, atomic absorption spectroscopy, and energy dispersive X‐ray spectroscopy. Subsequent pyrolysis resulted in nanoscale monoclinic bismuth vanadate that showed a high photocatalytic activity. The photocatalytic decomposition of model pollutants such as rhodamine B (RhB), methyl orange, methylene blue, and orange G under visible‐light irradiation using the as‐prepared bismuth vanadate samples was studied with a focus on the influence of the agglomeration behavior. The interplay between the photooxidation of RhB, induced by the excitation of the catalyst using visible light, and the photosensitized decomposition pathway is demonstrated by degradation experiments in solution and the solid state.

The alkoxide Bi[OCMe(2-CHS)] (1) is formed by the reaction of three equiv. of the alcohol HOCMe(2-CHS) with Bi(OBu) and subsequent hydrolysis provides the bismuth oxido cluster [BiO{OCMe(2-CHS)}] (2). In contrast, the reaction of Bi(OBu) and Bi[N(SiMe)] with the silanols HOSiMe(2-CHX) (X = O, S, Se, and NMe), HOSiMe(2-CHS-5-SiMe) and HOSiMe(3-CHS) leads to the formation of tris(heteroaryl)bismuthines Bi(2-CHX-5-R) [where X = O, R = H (3); X = S, R = H (4); X = S, R = SiMe (5); X = NMe, R = H (6); X = Se, R = H (7)] and Bi(3-CHS) (8). For the silanols, bismuth-carbon bond formation is observed rather than silanol-alcoholate or silanol-amide exchange. The structures of compounds 1, 2, and 4-7a in the solid state were established by single crystal X-ray diffraction and all compounds except 5 show London dispersion type bismuthπ heteroarene interactions. For the bismuthine Bi(2-CHSe) (7), two polymorphs were isolated depending on the conditions of crystallization. At 8 °C, polymorph I (7a) crystallizes from an n-hexane solution in the triclinic space group P1[combining macron], whereas polymorph II (7b) crystallizes at 20 °C from a CHCl/n-pentane solution in the monoclinic space group P2/c. The heteroaryl bismuthines 3 and 4 exhibit 2D network structures as a result of bismuthπ heteroarene interactions, whereas for the pyrrole derivative 6 the dispersion type interactions provide separated dimers.