From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry

Müller A, Gouzerh P (2012)
Chemical Society Reviews 41(22): 7431-7463.

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Following Nature's lessons, today chemists can cross the boundary of the small molecule world to construct multifunctional and highly complex molecular nano-objects up to protein size and even cell-like nanosystems showing responsive sensing. Impressive examples emerge from studies of the solutions of some oxoanions of the early transition metals especially under reducing conditions which enable the controlled linking of metal-oxide building blocks. The latter are available from constitutional dynamic libraries, thus providing the option to generate multifunctional unique nanoscale molecular systems with exquisite architectures, which even opens the way towards adaptive and evolutive (Darwinian) chemistry. The present review presents the first comprehensive report of current knowledge (including synthesis aspects not discussed before) regarding the related giant metal-oxide clusters mainly of the type {Mo57M6'} (M' = Fe-III, V-IV) (torus structure), {M72M30'} (M = Mo, M' = V-IV, Cr-III, Fe-III, Mo-V), {M72Mo60} (M = Mo, W) (Keplerates), {Mo-154}, {Mo-176}, {Mo-248} ("big wheels''), and {Mo-368} ("blue lemon") - all having the important transferable pentagonal {(M)M-5} groups in common. These discoveries expanded the frontiers of inorganic chemistry to the mesoscopic world, while there is probably no collection of discrete inorganic compounds which offers such a versatile chemistry and the option to study new phenomena of interdisciplinary interest. The variety of different properties of the sphere-and wheel-type metal-oxide-based clusters can directly be related to their unique architectures: The spherical Keplerate-type capsules having 20 crown-ether-type pores and tunable internal functionalities allow the investigation of confined matter as well as that of sphere-surface-supramolecular and encapsulation chemistry - including related new aspects of the biologically important hydrophobic effects - but also of nanoscale ion transport and separation. The wheel-type molybdenum-oxide clusters exhibiting complex landscapes do not only have well-defined reaction sites but also show unprecedented adaptability regarding the integration of various kinds of matter. Applications in different fields, e. g. in materials science and catalysis including those in small spaces, investigated by several groups, are discussed while possible directions for future work are outlined.
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Müller A, Gouzerh P. From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry. Chemical Society Reviews. 2012;41(22):7431-7463.
Müller, A., & Gouzerh, P. (2012). From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry. Chemical Society Reviews, 41(22), 7431-7463.
Müller, A., and Gouzerh, P. (2012). From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry. Chemical Society Reviews 41, 7431-7463.
Müller, A., & Gouzerh, P., 2012. From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry. Chemical Society Reviews, 41(22), p 7431-7463.
A. Müller and P. Gouzerh, “From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry”, Chemical Society Reviews, vol. 41, 2012, pp. 7431-7463.
Müller, A., Gouzerh, P.: From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry. Chemical Society Reviews. 41, 7431-7463 (2012).
Müller, Achim, and Gouzerh, Pierre. “From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry”. Chemical Society Reviews 41.22 (2012): 7431-7463.
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37 Citations in Europe PMC

Data provided by Europe PubMed Central.

Porous capsules with a large number of active sites: nucleation/growth under confined conditions.
Garai S, Rubcic M, Bogge H, Gouzerh P, Muller A., Chemistry 21(11), 2015
PMID: 25653204
Hedgehog-shaped {Mo368} cluster: unique electronic/structural properties, surfactant encapsulation and related self-assembly into vesicles and films.
Garai S, Merca A, Bhowmik S, El Moll H, Li H, Haso F, Nogueira H, Liu T, Wu L, Gouzerh P, Muller A., Soft Matter 11(12), 2015
PMID: 25629447
Modular molecules: site-selective metal substitution, photoreduction, and chirality in polyoxometalate hybrids.
Vonci M, Akhlaghi Bagherjeri F, Hall PD, Gable RW, Zavras A, O'Hair RA, Liu Y, Zhang J, Field MR, Taylor MB, Du Plessis J, Bryant G, Riley M, Sorace L, Aparicio PA, Lopez X, Poblet JM, Ritchie C, Boskovic C., Chemistry 20(43), 2014
PMID: 25204640
Keplerate cluster (Mo-132) mediated electrostatic assembly of nanoparticles.
Gooch J, Jalan AA, Jones S, Hine CR, Alam R, Garai S, Maye MM, Muller A, Zubieta J., J Colloid Interface Sci 432(), 2014
PMID: 25086388
Water repellency in hydrophobic nanocapsules--molecular view on dewetting.
Muller A, Garai S, Schaffer C, Merca A, Bogge H, Al-Karawi AJ, Prasad TK., Chemistry 20(22), 2014
PMID: 24782303
Tracking "apolar" NMe4+ ions within two polyoxothiomolybdates that have the same pores: smaller clathrate and larger highly porous clusters in action.
Korenev VS, Boulay AG, Haouas M, Bannani F, Fedin VP, Sokolov MN, Terazzi E, Garai S, Muller A, Taulelle F, Marrot J, Leclerc N, Floquet S, Cadot E., Chemistry 20(11), 2014
PMID: 24519761
Which inorganic structures are the most complex?
Krivovichev SV., Angew. Chem. Int. Ed. Engl. 53(3), 2014
PMID: 24339343
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Grego A, Muller A, Weinstock IA., Angew. Chem. Int. Ed. Engl. 52(32), 2013
PMID: 23765614
Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M5}12Fe(III)30 (M = Mo(VI), W(VI)).
Kuepper K, Derks C, Taubitz C, Prinz M, Joly L, Kappler JP, Postnikov A, Yang W, Kuznetsova TV, Wiedwald U, Ziemann P, Neumann M., Dalton Trans 42(22), 2013
PMID: 23403844

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