Nitronyl nitroxides with thiol groups, NitRs, provide exciting opportunities for investigating the properties of magnetic SAMs on gold surfaces. Here we have employed periodic/molecular DFT calculations to study the energetics, structure, bonding and magnetic exchange of SAMs of nitronyl nitroxide radical thiols on Au(111). Two structures 4-(methylthio)phenyl nitronyl nitroxide (NitR-ASCH3), A ¼ phenyl, and 4-(methylthio)methyl phenyl nitronyl nitroxide (NitR-B-SCH3), B ¼ phenyl- CH2, have been chosen. The radical species of type NitR-B-S is found to be energetically favourable with the reconstructed 1 : 2 Auad/thiols ratio model being the most favored structure. The computed structures are consistent with the experimental data (STM, ToF-SIMS and EPR) reported earlier. The computed magnetic exchange interactions in the SAMs of nitronyl nitroxide radicals reveal a stronger than expected intramolecular coupling, revealing the non-innocent nature of the gold surface.

A DFT exploration of the organization of thiols on Au(111): a route to self-assembled monolayer of magnetic molecules / G.Rajaraman; A.Caneschi; D.Gatteschi; F.Totti. - In: JOURNAL OF MATERIALS CHEMISTRY. - ISSN 0959-9428. - STAMPA. - 20:(2010), pp. 10747-10754. [10.1039/C0JM02481C]

A DFT exploration of the organization of thiols on Au(111): a route to self-assembled monolayer of magnetic molecules

CANESCHI, ANDREA;GATTESCHI, DANTE;TOTTI, FEDERICO
2010

Abstract

Nitronyl nitroxides with thiol groups, NitRs, provide exciting opportunities for investigating the properties of magnetic SAMs on gold surfaces. Here we have employed periodic/molecular DFT calculations to study the energetics, structure, bonding and magnetic exchange of SAMs of nitronyl nitroxide radical thiols on Au(111). Two structures 4-(methylthio)phenyl nitronyl nitroxide (NitR-ASCH3), A ¼ phenyl, and 4-(methylthio)methyl phenyl nitronyl nitroxide (NitR-B-SCH3), B ¼ phenyl- CH2, have been chosen. The radical species of type NitR-B-S is found to be energetically favourable with the reconstructed 1 : 2 Auad/thiols ratio model being the most favored structure. The computed structures are consistent with the experimental data (STM, ToF-SIMS and EPR) reported earlier. The computed magnetic exchange interactions in the SAMs of nitronyl nitroxide radicals reveal a stronger than expected intramolecular coupling, revealing the non-innocent nature of the gold surface.
20
10747
10754
G.Rajaraman; A.Caneschi; D.Gatteschi; F.Totti
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2158/405223
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