MS35-P08 Engeneering novel poruos 3D metallacrown-frameworks, through the ligand periphery design Vittoria Marzaroli (University of Parma, Parma, Italy) Luciano Marchió (Department of Chemical Sciences, Life Sciences, and Environmental Sustainability, Università di Parma, Parma, Italy) Giulia Spigolon (Chemistry Department, University of Padova, Padova, Italy) Giulia Licini (Chemistry Department, University of Padova, Padova, Italy) Vincent L. Pecoraro (Chemistry Department, University of Michigan, Ann Arbor, United States of America) Matteo Tegoni (Department of Chemical Sciences, Life Sciences, and Environmental Sustainability, Università di Parma, Parma, Italy)email: vittoria.marzaroli@studenti.unipr.it

Metallacrowns are metallamacrocycles characterized by the (M-N-O)nconnectivity and originated by self-assembly of bischelating ligands (e.g. hydroxamic acids) and metal ions. Properties and structure of this class of compounds are tunable through a wise choice of the building blocks set. [1] Moreover a relatively large amount of metal ions are confined in a small molecular volume, resulting in peculiar chemical physical features, such as luminescence or single-molecule magnets behavior. [2] 

We present here three new metallacrowns-based materials, that were prepared using salicylhydroxamic acid derivatives as ligands and Mn(II/III) as metal ion.

The salicyhydroxamic acid (H3Shi) react with Mn, forming a tightly packed, not porous coordination polymer. The nodes are endeca-manganese clusters, resembling a 3-blade propeller, where each blade is a half of a 16-metallacrown-6. Both the amino (H3p-aShi) and the pyridyl (H3p-pyShi) derivatives result in a novel porous arrays having the same Mn11cluster node. The amino function of H3p-aShi drives the propellers to interact through sodium ions and supramolecular interactions (i.e. hydrogen bonds). The resulting architecture shows hexagonal channels, which correspond to 39 % of the unit cell volume. The pyridyl function of H3p-pyShi coordinates one Mn of the neighboring propeller. As a result H3p-pyShi originates a metallacrown-based network, which shows channels in all the three dimensions and has cavities corresponding to 55% of the unit cell volume. The array, shown in the Figure, can be considered a novel metal-organic-framework with an endeca-Mn node.

References:

[1] C. Atzeri, V. Marzaroli, M. Quaretti, J. R. Travis, L. Di Bari, C. M. Zaleski and M. Tegoni, Inorg. Chem., 2017, 56, 8257–8269.

[2] C. M. Zaleski, S. Tricard, E. C. Depperman, W. Wernsdorfer, T. Mallah, M. L. Kirk and V. L. Pecoraro, Inorg. Chem., 2011, 50, 11348–11352.

Keywords: metallacrown, metal-organic-frameworks, ligand-design