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Intermolecular Interaction and Magnetic Coupling Mechanism of a Mononuclear Nickel(II) Complex
Author(s) -
Pan Ning,
Wei RuiZheng,
Chi YanHui,
Shi JingMin,
Wei Wei,
Zhang YiQuan
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200560
Subject(s) - intermolecular force , ferromagnetism , stacking , crystallography , nickel , density functional theory , chemistry , antiferromagnetism , ion , magnetic susceptibility , crystal structure , octahedron , inductive coupling , condensed matter physics , materials science , computational chemistry , molecule , physics , organic chemistry , quantum mechanics
The mononuclear complex [Ni(HOphen)(OSO 3 )(H 2 O) 3 ] · 5H 2 O (HOphen = 1, 10‐phenanthrolin‐2‐ol) was prepared and its single structure was determined by X‐ray crystallography. In this complex, the Ni II ion has a distorted octahedral arrangement. Crystal structure analysis shows that two kinds of π–π stacking interactions and C–H ··· O short contact intermolecular interactions exist among the adjacent complexes. Fitting to the variable‐temperature magnetic susceptibility data gave the magnetic coupling constant, 2 J = –0.98 cm –1 . Theoretical calculations, based on density functional theory (DFT) coupling with the broken‐symmetry approach (BS), revealed that the π–π stacking magnetic coupling pathways resulted in weak ferromagnetic interactions with 2 J = 4.86 cm –1 and 2 J = 4.16 cm –1 , respectively, for the adjacent Ni II ions with separations of 8.568(19) Å and 8.749(32) Å, respectively; whereas the magnetic coupling pathway of the C–H ··· O short contact intermolecular interaction led to a weak antiferromagnetic interaction with 2 J = –17.62 cm –1 for the adjacent Ni II ions with a separation of 10.291(26) Å. The ferromagnetic coupling sign can be explained by the McConnell I spin‐polarization mechanism.