期刊
INORGANIC CHEMISTRY FRONTIERS
卷 4, 期 6, 页码 986-993出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7qi00023e
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资金
- FONDECYT [1140359]
- Project Millennium [RC120001]
- Academy of Finland [275845, 289179]
- Swedish Cultural Foundation in Finland
- Magnus Ehrnrooth Foundation
- Norwegian Research Council through the CoE Centre for Theoretical and Computational Chemistry [179568/V30, 231571/F20]
- Norwegian Supercomputing Program (NOTUR) [NN4654 K]
- Department of Chemistry
- School of Science of the Universidad de los Andes
[trans-Cu(mu-OH)(mu-dmpz)](6) (1) exhibits six Cu(II) centers effectively coupled through a ligand mediated mechanism leading to a diamagnetic ground state over a wide temperature range. Here we investigate further magneto-structural correlations based on the possible free electron precession along such a copper-based ring-like nanocoil mediated by bridging ligands. We find that in 1, mediated antiferro-magnetic coupling leads to characteristics that induce aromatic ring behavior through evaluation of both induced currents and shielding of cones from a relativistic density functional theory level. According to our gauge calculations including magnetically induced current densities and an induced magnetic field, a sizable ring current strength susceptibility is obtained for the cyclic Cu-N-N-Cu and Cu-O-Cu pathways, allowing a magnetic exchange between the copper centers. Our study suggests that [Cu-6(dmPz)(6)(OH)(6)] consisting of an aromatic ring structure displays aromaticity and superexchange along the Cu-O-Cu and Cu-N-N-Cu backbones, which accounts for 80% and 20% of the overall ring current strength susceptibility, respectively. This reveals the presence of particular aromatic ring characteristics in coordination compounds without a direct metal-metal bond, where several formally paramagnetic centers are antiferromagnetically-coupled through supporting ligands. We envisage that our findings can be extended to other examples depicting ligand-mediated interaction between metal centers.
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