Aromaticity introduced by antiferromagnetic ligand mediated metal-metal interactions. Insights from the induced magnetic response in [Cu-6(dmPz)(6)(OH)(6)]

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Molina , V , Rauhalahti , M , Hurtado , J , Fliegl , H , Sundholm , D & Munoz-Castro , A 2017 , ' Aromaticity introduced by antiferromagnetic ligand mediated metal-metal interactions. Insights from the induced magnetic response in [Cu-6(dmPz)(6)(OH)(6)] ' , Inorganic Chemistry Frontiers , vol. 4 , no. 6 , pp. 986-993 . https://doi.org/10.1039/c7qi00023e

Title: Aromaticity introduced by antiferromagnetic ligand mediated metal-metal interactions. Insights from the induced magnetic response in [Cu-6(dmPz)(6)(OH)(6)]
Author: Molina, V.; Rauhalahti, M.; Hurtado, J.; Fliegl, H.; Sundholm, D.; Munoz-Castro, A.
Other contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
Date: 2017-06-01
Language: eng
Number of pages: 8
Belongs to series: Inorganic Chemistry Frontiers
ISSN: 2052-1553
DOI: https://doi.org/10.1039/c7qi00023e
URI: http://hdl.handle.net/10138/307922
Abstract: [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.
Subject: INDEPENDENT CHEMICAL-SHIFTS
2-ELECTRON VALENCE INDEXES
INCLUDING ATOMIC ORBITALS
DENSITY-FUNCTIONAL THEORY
CU-II COMPLEXES
COPPER(II) COMPLEXES
ORGANIC FRAMEWORKS
CRYSTAL-STRUCTURE
H-1-NMR SPECTRA
BASIS-SETS
116 Chemical sciences
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