An Unprecedented Bird Nest Molybdenum(V) Cobalto‐Phosphate Nanosized Wheel Constructed from the [H55(Mo24O48)(Co4O)2Co16(PO4)42(py)6(EtOH)2(H2O)11]3− Anion

An unprecedented bird‐nest high‐nuclear molybdenum(V) cobalto‐phosphate nanosized wheel modified by imidazole (im) and pyridine (py), {[H55(Mo24O48)(Co4O)2Co16(PO4)42(py)6(EtOH)2(H2O)11]‐ @[(Him)2(Hpy)]}(N‐Et‐py)(H2PO4)(py)7(EtOH)⋅12 H2O (1), has been successfully synthesized by self‐assembly. The anionic huge wheel consists of two rare {Co4O} 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. [ABSTRACT FROM AUTHOR]