Agenda

19 Dic 2023 10:45

Molecular Gold Nanoclusters and the Hydrogen/Deuterium Puzzle

Aula Delta 0A, Campus Scientifico Via Torino

Prof. Flavio Maran, Department of Chemistry, University of Padova, Department of Chemistry, University of Connecticut, United States

Abstract: Substituent effects have never been studied by changing a very large number of identical substituents. This kind of study obviously requires the use of very special molecules where this kind of substitution is indeed possible. In this context, ultrasmall ligand-protected gold nanoclusters, such as Au25 (SR)18  where SR is a thiolate, provide the opportunity to test the combined effect of changing 18 identical ligands1,2 These systems are prepared with atomic precision, exhibit truly molecular properties, and their physicochemical, electrochemical, and electron transfer (ET) behaviors can be tuned by acting on both the metal and organic components.1-9 We prepared the first fully deuterated gold nanocluster, Au25 (SC4 D9 )18, and compared its electrochemical, ET, solid-state, and photophysical behaviors in comparison with those observed for the corresponding nondeuterated Au25 (SC4 H9)18 cluster. We found that the deuterated molecule exhibits several unexpected differences. For example, the rates of heterogeneous ET and, particularly, intercluster ET in films are lower; the rate by which two deuterated clusters react in films to form Au 38  is significantly lower than for Au25 (SC4 H9)18; single crystal X-ray crystallography evidences important differences also between the structures of Au25 (SC4 D9 )18  and Au25 (SC4 H9)18. These and further results indicate that deuterated thiolates are far from being noninnocent ligands. The observed effects may be relevant, e.g., to affect the behavior of nanoclusters when used as building blocks for hierarchical structures.10


References
[1] S. Antonello, G. Arrigoni, T. Dainese, M. De Nardi, G. Parisio, L. Perotti, A. René, A. Venzo, F.
Maran, ACS Nano, 8 (2014), 2788.
[2] S. Antonello, T. Dainese, F. Maran. Electroanal., 28 (2016) 2771.
[3] M. De Nardi, S. Antonello, D. Jiang, F. Pan, K. Rissanen, M. Ruzzi, A. Venzo, A. Zoleo, F. Maran.
ACS Nano, 8 (2014) 8505.
[4] S. Antonello, F. Maran. Curr. Opin. Electrochem., 2 (2017) 18.
[5] M. Agrachev, W. Fei, S. Antonello, S. Bonacchi, T. Dainese, A. Zoleo, M. Ruzzi, F. Maran. Chem.
Sci., 11 (2020) 3427.
[6] S. Antonello, T. Dainese, M. De Nardi, L. Perotti, F. Maran. ChemElectroChem, 3 (2016) 1237.
[7] W. Fei, S. Antonello, T. Dainese, A. Dolmella, M. Lahtinen, K. Rissanen, A. Venzo, F. Maran, J.
Am. Chem. Soc., 141 (2019) 16033.
[8] M. Agrachev, M. Ruzzi, A. Venzo, F. Maran, Acc. Chem. Res. 52 (2019), 44.
[9] M. Reato, T. Dainese, S. Antonello, F. Maran. Chem. Mater., 33 (2021) 4177.
[10] S. Bonacchi, S. Antonello, T. Dainese, F. Maran, Chem. Eur. J., 27 (2012) 30.

 

Orgsanized by Prof. Federico Polo

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Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari Venezia

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