Temperature-dependent zero-field splitting in a copper(II) dimer studied by EPR / Fedin Matvey V.,Zhilina Ekaterina F.,Chizhov Dmitrii L.,Apolonskaya Inna A.,Aleksandrov Grigory G.,Kiskin Mikhail A.,Sidorov Aleksei A.,Bogomyakov Artem S.,Romanenko Galina V.,Eremenko Igor L.,Novotortsev Vladimir M.,Charushin Valery N. // DALTON TRANSACTIONS. - 2013. - V. 42, l. 13. - P. 4513-4521.

ISSN/EISSN:

1477-9226 / нет данных

Type:

Article

Abstract:

We report on the synthesis and temperature-dependent magnetic properties observed in an exchange-coupled copper(II) dimer using X/Q-band Electron Paramagnetic Resonance (EPR) spectroscopy (9/34 GHz). It has been found that the zero-field splitting (D) in the dimer changes gradually by a factor close to two in the temperature range from T = 50 to 300 K. X-ray diffraction data show that this dimer consists of two five-coordinated copper ions, one of which has a highly asymmetric geometry intermediate between square pyramid and trigonal bipyramid. The copper-copper distance in the dimer is temperature-independent, whereas the degree of trigonality in an asymmetric unit decreases as the temperature is lowered. Therefore we suppose that the observed dependence D(T) originates from the interplay of different exchange interaction pathways driven by these thermal changes. Magnetic susceptibility measurements reveal weak ferromagnetic interactions, whose anisotropic parts should indeed be very sensitive to the subtle changes in the geometry and may result in apparent D(T). Apart from being a very unusual example of magneto-structural correlations, this and similar dimeric systems can be considered as an interesting type of new materials exhibiting strongly temperature-dependent magnetic properties.

Author keywords:

JAHN-TELLER DISTORTIONS; ELECTRON-PARAMAGNETIC-RESONANCE; SUBSTITUTED NITRONYL NITROXIDE; CRYSTAL-STRUCTURE; MOLECULAR MAGNETS; BREATHING CRYSTALS; SPIN-TRANSITION; INTERCLUSTER EXCHANGE; BRIDGING LIGAND; COMPLEXES

DOI:

10.1039/c2dt32697c

Web of Science ID:

ISI:000316294400025

Соавторы в МНС:

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Другие поля

Поле	Значение
Publisher	ROYAL SOC CHEMISTRY
Address	THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND
Language	English
Keywords-Plus	JAHN-TELLER DISTORTIONS; ELECTRON-PARAMAGNETIC-RESONANCE; SUBSTITUTED NITRONYL NITROXIDE; CRYSTAL-STRUCTURE; MOLECULAR MAGNETS; BREATHING CRYSTALS; SPIN-TRANSITION; INTERCLUSTER EXCHANGE; BRIDGING LIGAND; COMPLEXES
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Inorganic \& Nuclear
Author-Email	mfedin@tomo.nsc.ru
ResearcherID-Numbers	Kiskin, Mikhail/J-3596-2012 Bogomyakov, Artem/A-7079-2014 Sidorov, Alexey/C-1652-2013 Eremenko, Igor/N-7242-2015 Fedin, Matvey/F-3807-2016
ORCID-Numbers	Kiskin, Mikhail/0000-0002-8782-1308 Bogomyakov, Artem/0000-0002-6918-5459 Eremenko, Igor/0000-0001-6861-1404 Fedin, Matvey/0000-0002-0537-5755 Romanenko, Galina/0000-0001-8852-2759
Funding-Acknowledgement	RFBR {[}12-03-33010, 11-03-00158, 11-03-00027, 11-03-00556, 08-03-90717, 09-03-90717, 10-03-90732]; Council on Grants of the President of the Russian Federation {[}NSh-2357.2012.3, NSh-1670.2012.3]; Russian Academy of Sciences; Siberian Branch of the Russian Academy of Sciences; RF Ministry of Education and Science {[}8436, 8456]
Funding-Text	We thank Dr Sergey Veber and Prof. Elena Bagryanskaya (ITC) for fruitful discussions. We thank Prof. Alexander Schnegg (Helmholtz Zentrum Berlin) for the opportunity to perform test measurements at 263 GHz, and Ms Irina Drozdyuk (ITC) for carrying out these measurements. This work was supported by RFBR (No. 12-03-33010, 11-03-00158, 11-03-00027, 11-03-00556, 08-03-90717, 09-03-90717, 10-03-90732), the Council on Grants of the President of the Russian Federation (grants NSh-2357.2012.3, NSh-1670.2012.3), the Russian Academy of Sciences, the Siberian Branch of the Russian Academy of Sciences and RF Ministry of Education and Science (No. 8436 and 8456).
Number-of-Cited-References	60
Usage-Count-Last-180-days	2
Usage-Count-Since-2013	30
Journal-ISO	Dalton Trans.
Doc-Delivery-Number	108LK