Computational Studies on SAMs of {Mn-6} SMMs on Au(111): Do Properties Change upon Grafting?

Single molecule magnets (SMM) adsorbed on surfaces as magnetic building blocks represent a hot topic of research in the area of molecular magnetism. Indeed, the understanding the properties of molecules on surface is extremely challenging as atomistic structures are not readily available. In this regard, theoretical studies as reliable tool to reproduce and predict the structure and the magnetic ground state of SMMs in the bulk phase and adsorbed on a surface, should be considered very appealing. In this framework, we report a periodic density functional (DF) study on two {Mn-6} SMM complexes of general formula [Mn(III)(6)O-2(R-sao)(6)(O2C-th)(2)L], where HO2C-th=3-thiophene carboxylic acid, saoH(2) = salicylaldoxime, R = H and L = (EtOH)(4) (1) or R = Et and L = (EtOH)(4)(H2O)(2) (2), performed to ascertain the structure of their self-assembled monolayers (SAM) on the Au(111) surface. Their magnetic properties in vacuum and in the adsorbed state have also been computed and our results clearly demonstrate that the grafting process is expected to not be a smooth one as it alters their bulk structure and, consequently, their magnetic properties