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Magnetyczne oddziaływania nadwymienne przez wiązania wodorowe

Korabik M.

Wiadomości Chemiczne

2008

[Z] 62, 5-6

449-478

Hydrogen bonds play a key role in interactions in biological structures, supramolecular chemistry, and crystal engineering [28, 29]. The development of supramolecular structure created by hydrogen bonds is a new challenge for the synthesis of materials, in order to study their magnetic behaviour [59, 62]. A role played by hydrogen bonds in the transmission of magnetic interactions is still not fully understood, but the number of magnetically coupled hydrogen-bonded systems is growing. The present paper describes magnetic properties of copper(II) complexes [33] with nitrobenzoate and salicylate ligands where the system of hydrogen bonds O-HźźźO is the only path of magnetic interaction. Magnetic measurements in the temperature range 1.8-300 K show magnetic phase-transition at 6 K to antiferromagnetically coupled CuII dimers with singlet-tryplet energy gap 2J = -6.26 cm-1. A variety of different supramolecular hydrogen bond structures [27, 33-52, 57-62] and significant changes in their magnetic properties were analyzed to show the role of hydrogen bonds in magnetic interactions. Magnetostructural correlation has been made taking into account both covalently bridging ligand and the existence of intermolecular hydrogen bonds. An evidence for hydrogen-bond-mediated exchange coupling has been observed in magnetic study as well as in DFT calculations [40, 48]. Intermolecular interaction has been generally treated as a nuance, but today, it has established itself as an important functional tool, tunable at will [59] in the design of nanosized magnetic materials and their dimensionally-expanded compounds [57-62]. Intermolecular magnetic exchange interactions through hydrogen bonds, can have a large influence on the quantum properties of single molecular magnets SMMs [59]. Hydrogen bonding leads to coupling of the magnetic effects of individual SMMs units and to different quantum behaviour. Even very weak hydrogen bond inter-molecular interactions demonstrate a possibility of switching from an original nanosized magnetic system to a correlated system, for example, from single molecule magnet SMM to single chain magnet SCM or from such nanosized magnets to a bulk magnet [59].