An Unprecedented Bird Nest Molybdenum(V) Cobalto-Phosphate Nanosized Wheel Constructed from the [H55 (Mo24 O48 )(Co4 O)2 Co16 (PO4 )42 (py)6 (EtOH)2 (H2 O)11 ]3- Anion.

An unprecedented bird-nest high-nuclear molybdenum(V) cobalto-phosphate nanosized wheel modified by imidazole (im) and pyridine (py), {[H55 (Mo24 O48 )(Co4 O)2 Co16 (PO4 )42 (py)6 (EtOH)2 (H2 O)11 ]- @[(Him)2 (Hpy)]}(N-Et-py)(H2 PO4 )(py)7 (EtOH)⋅12 H2 O (1), has been successfully synthesized by self-assembly. The anionic huge wheel consists of two rare {Co4 O} squares, four {Co4 } tetramers, four {Mo4 } tetramers and four {Mo2 } dimers, linked by bridging oxygen atoms and [PO4 ] 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(NO3 )2 with the O2 production of 205 μmol during 6 h in the absence of the [Ru(bpy)3 ]2+ photosensitizer.