With appropriate choice of ligands, Mn 3 -based single-molecule magnets (SMMs) can be covalently linked to form SMM dimers that exhibit either ferromagnetic (FM) or antiferromagnetic (AFM) ground state. We present here results of density functional theory (DFT)-based calculations that elucidate the effect of two different types of support, graphene and two-dimensional hexagonal boron nitride (h-BN), on the electronic structure and magnetic properties of the ligated Mn 3 dimers. Our calculations for the spin per Mn 3 monomer of both the FM and AFM configurations of the isolated Mn 3 dimers in the gas phase agree with experimental results (S = 6) when the dimers are explicitly charged to a +2 state, the charged state found in experimental observations. Following the determination of the most stable configuration of each dimer on graphene and h-BN, the analysis of their spin reveals that their magnetic properties are not noticeably affected when adsorbed on these two-dimensional materials. The charge density, charge transfer, and binding analysis reveals that the dimers are physisorbed on both graphene and h-BN through van der Waals interactions, with charge transfer taking place in the case of graphene only. Our results provide insights into the design of proposed experiments for measuring transport properties of these AFM and FM dimers and the critical role played by graphene and h-BN as supports.

Two thiophene-based monocyclic receptors L1 and L2 have been studied for phosphate binding in solutions (D2O and DMSO-d6) by 1H NMR and 31P NMR titrations, and in the solid state by single crystal X-ray analysis. Results from 1H NMR titrations suggest that the ligands bind phosphate anions in a 1:2 binding mode in DMSO-d6, with the binding constants of 5.25 and 4.20 (in log K), respectively. The binding of phosphate to L1 and L2 was further supported by 31P NMR in D2O at pH = 5.2. The crystal structure of the phosphate complex of L1 reveals unambiguous proof for the formation of a ditopic complex via multiple hydrogen bonds from NH···O and CH···O interactions.