@misc{10481/97873,
year = {2024},
month = {12},
url = {https://hdl.handle.net/10481/97873},
abstract = {Abstract: Inspired by the reported crystal structure of compound 1, we aimed to synthesize and
determine the structure of compound 2, where two imidazolium (H2im+) ions serve as diamagnetic
countercations. Here, we report the thermal stabilities, FT–IR, visible, and RSE spectra, as well as the
magnetic properties of both compounds. In these structures, μ-EDTA acts as a pentadentate chelator
for both terminal Cu centers within the centrosymmetric linear trinuclear anion. The Cu(μ-EDTA)
chelates bind to the central Cu(Him)4 unit in subtly different ways: in compound 1, μ-EDTA has a
free acetate arm and binds the central Cu(II) center through a syn,anti-carboxylate group. In contrast,
in compound 2, the non-chelating acetate arm serves as a monodentate O-donor to the central Cu(II)
atom, increasing the Cu(terminal)···Cu(central) distance from 6.08 Å in 1 to 6.80 Å in 2. Additionally,
pairs of H2im+ ions in compound 2 display antiparallel π-stacking interactions. We conclude that the
H2im+ counterions in compound 2 enable the magnetic isolation of the nearly identical trinuclear
anion present in both compounds. DFT calculations further support the role of different interactions
in stabilizing each crystal structure. In compound 2, dominant contributions from N–H···O hydrogen
bonds and π-stacking interactions are accompanied by other, less conventional interactions, such as
multiple C–H···O contacts and an O···CO(π-hole) interaction within the trinuclear anion.},
organization = {Spain Ministry of Science, Innovation and Universities
(MICIU/AEI of Spain; projects PID2020-115637GB-I00 and PID2023-148453NB-I00, FEDER
funds)},
organization = {MICINN of Spain project PID2023-151538NB-I00 FEDER, Project B-FQM-478-UGR20 (FEDERUniversidad
de Granada, Spain)},
organization = {Research Group FQM-283 (Junta de Andalucía, Spain)},
publisher = {MDPI},
keywords = {copper(II)},
keywords = {linear trinuclear complex},
keywords = {crystal structure},
title = {Magnetic Isolation of the Linear Trinuclear Anion in [Cu(Him)6] {Cu(Him)4[Cu(μ-EDTA)(Him)]2}·6H2O (1) as the Novel Imidazolium(+) Salt (H2im)2[Cu(Him)4{(μ-EDTA)Cu(Him)}2]· 2H2O (2)—A Comparative Look to Their Crystal Structures, Thermal, Spectral and Magnetic Properties and DFT Calculations},
doi = {10.3390/ijms252313130},
author = {Belmont Sánchez, Jeannette Carolina and Choquesillo Lazarte, Duane and Frontera, Antonio and Lezama, Luis and Castiñeiras, Alfonso and Niclos Gutiérrez, Juan},
}