An Unprecedented Bird Nest Molybdenum(V) Cobalto-Phosphate Nanosized Wheel Constructed from the [H (Mo O )(Co O) Co (PO ) (py) (EtOH) (H O) ] Anion.

An unprecedented bird-nest high-nuclear molybdenum(V) cobalto-phosphate nanosized wheel modified by imidazole (im) and pyridine (py), {[H (Mo O )(Co O) Co (PO ) (py) (EtOH) (H O) ]- @[(Him) (Hpy)]}(N-Et-py)(H PO )(py) (EtOH)⋅12 H O (1), has been successfully synthesized by self-assembly. The anionic huge wheel consists of two rare {Co O} squares, four {Co } tetramers, four {Mo } tetramers and four {Mo } dimers, linked by bridging oxygen atoms and [PO ] groups and encloses two imidazolium cations and a protonated pyridium for charge balance. Surprisingly, 1 represents the first twisted wheel-shaped cluster with a record high-nuclear molybdenum(V) cobalto-phosphate. The delocalized electron effects of the cluster are enhanced with the help of coordinated py ligands, which endows 1 with an excellent third-order nonlinear optical (NLO) response. Additionally, 1 also shows a better photocatalytic water oxidation activity than Co(NO ) with the O production of 205 μmol during 6 h in the absence of the [Ru(bpy) ] photosensitizer.