Journal
DALTON TRANSACTIONS
Volume 41, Issue 6, Pages 1776-1785Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1dt11293g
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Funding
- National Research Foundation of Korea
- Korean Government [2011-0003264]
- Priority Research Centers through the National Research Foundation of Korea (NRF)
- Ministry of Education, Science and Technology [NRF20110018396]
- PAL [2010-3063-03]
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Five Fe(III) Mn(III) bimetallic compounds [Fe(iqc)(CN)(3)][Mn(5-Xsalen)]center dot pMeOH center dot qMeCN center dot rH(2)O [Hiqc = N-(quinolin-8-yl)isoquinoline-1-carboxamide; salen = N,N'-ethylenebis(salicylideneiminato) dianion; X = H(2), F(3, 3a), Cl(4), Br(5)] were prepared by assembling a newly designed mer-Fe tricyanide (Ph4P)[Fe(iqc)(CN)(3)]center dot 0.5H(2)O (1) and the respective Mn Schiff bases Mn(5-Xsalen)(+). Compounds 2-4 show linear chain structures in which trans-positioned cyanides of the Fe precursor bridge neighbouring Mn atoms, while 5 is a zigzag chain coordination polymer where two cyanide groups of the precursor in the cis mode act as bridges. The structural change from linear to zigzag may arise from the size effect of the halogens. The reversible structural transformation occurs between 3 and 3a upon the solvation-desolvation protocol and the corresponding magnetic behaviours are affected. Furthermore, in 4 and 5, the helical chains are established through hydrogen bonding of solvent molecules. From a magnetostructural point of view, within the linear chain system, the ferromagnetic coupling in 2, contrary to antiferromagnetic interactions in 3-4, is associated with the large torsion angle of C-eq-Fe-Mn-N(O)(eq) (eq = equatorial) as well as almost the linear Mn-N C angle.
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