Chirality can make electrochemistry even smarter, endowing it with a superior level of selectivity. In fact, chiral electrochemistry implies the ability to discriminate and possibly also quantify enantiomers of chiral molecules, in situ and with no preliminary separation steps, for analytical purposes; and to selectively activate or obtain the desired enantiomer of a chiral molecule, for synthetic purposes; moreover, a chiral electrochemical interphase can act as a spin filter, since electrons in rototranslational motion to/from the electrode surface are truly chiral objects. Thus chiral electrochemistry represents an attractive area with a huge applicative potential, although mostly unexploited so far, in spite of many proposed approaches. [1] In this context, the inherent chirality concept can provide the breakthrough. In fact, it implies chirality and key functional properties, like electroactivity, to originate from the same structural element, which can coincide with the whole backbone of the chiral selector, featuring a tailored torsion. Such unique threefold identity can endow the selector with extraordinary chirality manifestations. Unprecedented enantiorecognition in terms of large potential differences was indeed recently observed in voltammetry experiments, implementing inherent chirality in electrochemical interphases in terms of either (a) enantiopure electrode surfaces based on inherently chiral heterocycle-based electroactive oligomer films [2-5] or (b) highly ordered enantiopure media based on inherently chiral molecular salts (either as bulk ionic liquids or as additives in achiral ionic liquids)[6,7] The property appears of general character, a given selector being effective with quite different chiral probes, and viceversa. But such enantioselectivity has an even more wider character than that. In fact, the features of inherently chiral molecular materials can also make them outstandingly selective towards the two specular circular components of plane polarized light, resulting in outstanding chiroptical properties in both adsorption (circular dichroism) and emission (circularly polarized luminescence), even electrochemically modulable.[2,4,5] Furthermore, they could discriminate a vs b electrons in rototranslational motion to/from the electrode surface, which they are truly chiral objects; and impressive features have been recently observed in magnetoelectrochemistry experiments.[8] Such first thrilling evidences suggest fascinating correlations worthy to be explored among chiral electrochemistry, polarized light and spin magnetic moments. Dedicated to professor Armando Gennaro, an outstanding teacher in science and in life Support by Regione Lombardia, Fondazione Cariplo and Università degli Studi di Milano is gratefully acknowledged. [1] S. Arnaboldi, M. Magni, P. R. Mussini, Curr. Opin. Electrochem., 2018, 8, 60–72. [2] F. Sannicolò, S. Arnaboldi, T. Benincori, V. Bonometti, R. Cirilli, L. Dunsch, W. Kutner, G. Longhi, P.R. Mussini, M. Panigati, M. Pierini, S. Rizzo, Angew. Chem. Int. Ed. 2014, 53, 2623-2627. [3] S. Arnaboldi, T. Benincori, R. Cirilli, W. Kutner, M. Magni, P.R. Mussini, K. Noworyta, F. Sannicolò, Chem. Science 2015, 6, 1706-1711. [4] S.Arnaboldi, T. Benincori, A. Penoni, L. Vaghi, R. Cirilli, S. Abbate, G. Longhi, G. Mazzeo, S. Grecchi, M. Panigati, P. R. Mussini, Chem. Sci. 2019, 2708-2717 [5] S. Arnaboldi, S. Cauteruccio, S. Grecchi, T. Benincori, M. Marcaccio, A. Orbelli Biroli, G. Longhi, E. Licandro, P.R. Mussini, Chem.Sci. 6, 2019, 1706-1711 [6] S. Rizzo, S. Arnaboldi, V. Mihali, R. Cirilli, A. Forni, A. Gennaro, A.A. Isse, M. Pierini, P.R. Mussini, F. Sannicolò, Angew. Chem. Int. Ed. 2017, 56, 2079-2082. [7] S. Rizzo, S.Arnaboldi, R. Cirilli, A. Gennaro, A. A. Isse, F. Sannicolò, P. R. Mussini, Electrochem. Comm. 2018, 89, 57-61. [8] T. Benincori, D. Arnaboldi, M.Magni, S. Grecchi, R. Cirilli, C. Fontanesi, P.R. Mussini, Chem. Science 2019, 10, 2750-2757.

Powerful, Versatile Inherent Chirality at Electrochemical Interphases / P.R. Mussini. ((Intervento presentato al convegno Electrochimica Colloquia tenutosi a Padova nel 2020.

Powerful, Versatile Inherent Chirality at Electrochemical Interphases

P.R. Mussini
2020

Abstract

Chirality can make electrochemistry even smarter, endowing it with a superior level of selectivity. In fact, chiral electrochemistry implies the ability to discriminate and possibly also quantify enantiomers of chiral molecules, in situ and with no preliminary separation steps, for analytical purposes; and to selectively activate or obtain the desired enantiomer of a chiral molecule, for synthetic purposes; moreover, a chiral electrochemical interphase can act as a spin filter, since electrons in rototranslational motion to/from the electrode surface are truly chiral objects. Thus chiral electrochemistry represents an attractive area with a huge applicative potential, although mostly unexploited so far, in spite of many proposed approaches. [1] In this context, the inherent chirality concept can provide the breakthrough. In fact, it implies chirality and key functional properties, like electroactivity, to originate from the same structural element, which can coincide with the whole backbone of the chiral selector, featuring a tailored torsion. Such unique threefold identity can endow the selector with extraordinary chirality manifestations. Unprecedented enantiorecognition in terms of large potential differences was indeed recently observed in voltammetry experiments, implementing inherent chirality in electrochemical interphases in terms of either (a) enantiopure electrode surfaces based on inherently chiral heterocycle-based electroactive oligomer films [2-5] or (b) highly ordered enantiopure media based on inherently chiral molecular salts (either as bulk ionic liquids or as additives in achiral ionic liquids)[6,7] The property appears of general character, a given selector being effective with quite different chiral probes, and viceversa. But such enantioselectivity has an even more wider character than that. In fact, the features of inherently chiral molecular materials can also make them outstandingly selective towards the two specular circular components of plane polarized light, resulting in outstanding chiroptical properties in both adsorption (circular dichroism) and emission (circularly polarized luminescence), even electrochemically modulable.[2,4,5] Furthermore, they could discriminate a vs b electrons in rototranslational motion to/from the electrode surface, which they are truly chiral objects; and impressive features have been recently observed in magnetoelectrochemistry experiments.[8] Such first thrilling evidences suggest fascinating correlations worthy to be explored among chiral electrochemistry, polarized light and spin magnetic moments. Dedicated to professor Armando Gennaro, an outstanding teacher in science and in life Support by Regione Lombardia, Fondazione Cariplo and Università degli Studi di Milano is gratefully acknowledged. [1] S. Arnaboldi, M. Magni, P. R. Mussini, Curr. Opin. Electrochem., 2018, 8, 60–72. [2] F. Sannicolò, S. Arnaboldi, T. Benincori, V. Bonometti, R. Cirilli, L. Dunsch, W. Kutner, G. Longhi, P.R. Mussini, M. Panigati, M. Pierini, S. Rizzo, Angew. Chem. Int. Ed. 2014, 53, 2623-2627. [3] S. Arnaboldi, T. Benincori, R. Cirilli, W. Kutner, M. Magni, P.R. Mussini, K. Noworyta, F. Sannicolò, Chem. Science 2015, 6, 1706-1711. [4] S.Arnaboldi, T. Benincori, A. Penoni, L. Vaghi, R. Cirilli, S. Abbate, G. Longhi, G. Mazzeo, S. Grecchi, M. Panigati, P. R. Mussini, Chem. Sci. 2019, 2708-2717 [5] S. Arnaboldi, S. Cauteruccio, S. Grecchi, T. Benincori, M. Marcaccio, A. Orbelli Biroli, G. Longhi, E. Licandro, P.R. Mussini, Chem.Sci. 6, 2019, 1706-1711 [6] S. Rizzo, S. Arnaboldi, V. Mihali, R. Cirilli, A. Forni, A. Gennaro, A.A. Isse, M. Pierini, P.R. Mussini, F. Sannicolò, Angew. Chem. Int. Ed. 2017, 56, 2079-2082. [7] S. Rizzo, S.Arnaboldi, R. Cirilli, A. Gennaro, A. A. Isse, F. Sannicolò, P. R. Mussini, Electrochem. Comm. 2018, 89, 57-61. [8] T. Benincori, D. Arnaboldi, M.Magni, S. Grecchi, R. Cirilli, C. Fontanesi, P.R. Mussini, Chem. Science 2019, 10, 2750-2757.
feb-2020
Settore CHIM/01 - Chimica Analitica
Settore CHIM/02 - Chimica Fisica
Settore CHIM/06 - Chimica Organica
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