Heterometallic complexes combining {[}Mn-III(salpn)](+) and {[}Fe(CN)(6)](4-) units as the products of reactions between {[}Mn-III(salpn)(H2O)C(CN)(3)] and {[}Fe(CN)(6)](3-/4-) / Kopotkov Vyacheslav A.,Yagubskii Eduard B.,Simonov Sergey V.,Zorina Leokadiya V.,Starichenko Denis V.,Korolyov Alexander V.,Ustinov Vladimir V.,Shvachko Yuri N. // NEW JOURNAL OF CHEMISTRY. - 2014. - V. 38, l. 9. - P. 4167-4176.

ISSN/EISSN:

1144-0546 / 1369-9261

Type:

Article

Abstract:

The reaction of {[}Fe(III)(CN)(6)](3-) with neutral {[}Mn(salpn)(H2O)C(CN)(3)] (salpn: N,N'-propylenebis(salicylideneiminato)) (1) produces two new heterometallic complexes {[}\{Mn-III(salpn)(H2O)\}(2)\{Mn-III(salpn)(H2O)(0.7)(CH3OH)(0.3)\}(2)Fe -II(CN)(6)]center dot n(H2O/CH3OH) (2) and {[}\{Mn-III(salpn)\}(4)\{Mn-III(salpn)(H2O)\}(2)Fe-II(CN)(6)]\{C(CN)(3)\ }(2)center dot 4H(2)O (3), which are characterized by single-crystal X-ray diffraction. In this reaction, the {[}C(CN)3](-) ligand reduces Fe(III) to Fe(II). Complex 3 can be prepared directly using hexacyanoferrate(II). One more complex containing the hexacyanoferrate(II), {[}\{Mn-III(salpn)(CH3OH)(0.67)(H2O)(0.33)\}(6)Fe-II(CN)(6)]\{ClO4\}(2)c enter dot 8H(2)O (4), is obtained in the reaction of {[}Fe(II)(CN)(6)](4-) with the cationic complex {[}Mn-2(salpn)(2)(H2O)(2)](ClO4)(2). The iron(II) centers in the complexes 2 and 4 are linked via cyano-bridges with the four and six {[}Mn-III(salpn)](+) fragments, respectively. The structure of 3 consists of the cyano-bridged {[}(Mn6FeII)-Fe-III] repeating units linked by double phenolate bridges into a one-dimensional polymeric chain. The magnetic properties of 3 indicate a ferromagnetic coupling between Mn-III centers in the double phenolate-bridged {[}Mn-III(salpn)](2) dinuclear subunits. Quantum calculations within the Heisenberg-Van Vleck model are performed giving the exchange constant J = 0.64 cm(-1) and the zero-field splitting parameter D = -3.5 +/- 0.5 cm(-1). The ac-susceptibility obeys the Arrhenius law with the activation energy E-a = 11.89 cm(-1).

Author keywords:

SCHIFF-BASE COMPLEXES; SINGLE-MOLECULE-MAGNET; CRYSTAL-STRUCTURE; CHAIN MAGNETS; MANGANESE(III) COMPLEXES; BIMETALLIC ASSEMBLIES; NETWORK STRUCTURES; BUILDING-BLOCKS; LIGANDS; FE

DOI:

10.1039/c4nj00427b

Web of Science ID:

ISI:000341065800018

Соавторы в МНС:

—

Другие поля

Поле	Значение
Month	SEP
Publisher	ROYAL SOC CHEMISTRY
Address	THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND
Language	English
EISSN	1369-9261
Keywords-Plus	SCHIFF-BASE COMPLEXES; SINGLE-MOLECULE-MAGNET; CRYSTAL-STRUCTURE; CHAIN MAGNETS; MANGANESE(III) COMPLEXES; BIMETALLIC ASSEMBLIES; NETWORK STRUCTURES; BUILDING-BLOCKS; LIGANDS; FE
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Multidisciplinary
Author-Email	slavaoven@mail.ru yagubski@icp.ac.ru zorina@issp.ac.ru yshvachko@ucdavis.edu
ResearcherID-Numbers	Starichenko, Denis/J-9813-2013 Alexander, Korolev/K-3036-2013 Ustinov, Vladimir/G-7501-2011
ORCID-Numbers	Starichenko, Denis/0000-0001-9481-538X Alexander, Korolev/0000-0002-5104-3997 Ustinov, Vladimir/0000-0002-5155-7947
Funding-Acknowledgement	RFBR {[}13-03-12418]; Presidium of the Russian Academy of Sciences {[}12M-23-2054, 1540.2014.2]
Funding-Text	This work was supported by the RFBR grant 13-03-12418 and Presidium of the Russian Academy of Sciences, project No. 12M-23-2054, grant for support of the leading scientific schools No. 1540.2014.2. We thank P. Yu. Barzilovich and K. A. Lyssenko for performing an X-ray experiment on a Bruker APEX II diffractometer. Y. N. Sh thanks Alex Mogilner and UC Davis for providing the visiting scholar position and computational resources.
Number-of-Cited-References	61
Usage-Count-Last-180-days	1
Usage-Count-Since-2013	14
Journal-ISO	New J. Chem.
Doc-Delivery-Number	AO1IM