Spin crossover and high spin electroneutral mononuclear iron(iii) Schiff base complexes involving terminal pseudohalido ligands

2015 ◽  
Vol 39 (1) ◽  
pp. 508-519 ◽  
Author(s):  
Petra Masárová ◽  
Pavel Zoufalý ◽  
Ján Moncol ◽  
Ivan Nemec ◽  
Ján Pavlik ◽  
...  

Six new Schiff-base complexes (1–6) with pseudohalido terminal ligands exhibits spin crossover or high spin state behaviour.

2020 ◽  
Vol 6 (2) ◽  
pp. 28
Author(s):  
Greg Brewer

A review of the tripodal Schiff base (SB) complexes of tris(2-aminoethyl)amine, Nap(CH2CH 2NH2)3 (tren), and a few closely related tripodal amines with Cr(II), Mn(III) (d4), Mn(II), Fe(III) (d5), Fe(II) (d6), and Co(II) (d7) is provided. Attention is focused on examination of key structural features, the M-Nimine, M-Namine, or M-O and M-Nap bond distances and Nimine-M-N(O) bite and C-Nap-C angles and how these values correlate with spin state selection and spin crossover (SCO) behavior. A comparison of these experimental values with density functional theory calculated values is also given. The greatest number, 132, of complexes is observed with cationic mononuclear iron(II) in a N6 donor set, Fe(II)N6. The dominance of two spin states, high spin (HS) and low spin (LS), in these systems is indicated by the bimodal distribution of histogram plots of Fe(II)-Nimine and Fe(II)-Nazole/pyridine bond distances and of Nimine–Fe(II)-Nazole/pyridine and C-Nap-C bond angles. The values of the two maxima, corresponding to LS and HS states, in each of these histograms agree closely with the theoretical values. The iron(II)-Nimine and iron(II)-Nazole/pyridine bond distances correlate well for these complexes. Examples of SCO complexes of this type are tabulated and a few of the 20 examples are discussed that exhibit interesting features. There are only a few mononuclear iron(III) cationic complexes and one is SCO. In addition, a significant number of supramolecular complexes of these ligands that exhibit SCO, intervalence, and chiral recognition are discussed. A summary is made regarding the current state of this area of research and possible new avenues to explore based on analysis of the present data.


2014 ◽  
Vol 67 (11) ◽  
pp. 1574 ◽  
Author(s):  
Darunee Sertphon ◽  
David J. Harding ◽  
Phimphaka Harding ◽  
Keith S. Murray ◽  
Boujemaa Moubaraki ◽  
...  

A new sterically bulky Schiff base ligand, N-(8-quinolyl)-5-tert-butylsalicylaldimine (Hqsal-5-tBu) has been prepared and a series of FeIII complexes, [Fe(qsal-5-tBu)2]Y (Y = Cl 1, ClO4 2, NO3 3, BF4 4) utilising this ligand are reported and fully characterised. UV-vis spectroscopic and electrochemical studies indicate that 1–4 are high spin (HS) in solution at room temperature and further suggest that the tBu group only slightly alters the electronic properties of 1–4 compared with related [Fe(qsal-5-X)2]+ systems. The structures of [Fe(qsal-5-tBu)2]Cl·4MeOH·H2O 1, [Fe(qsal-5-tBu)2]ClO4·MeOH 2, and [Fe(qsal-5-tBu)2]NO3 3 determined at 100 K reveal HS FeIII centres in all cases. Four-fold parallel aryl embraces and π–π interactions serve to link the cations forming 2D sheets mirroring the motifs found in other [Fe(qsal-5-X)2]+ complexes. Despite this the tBu group causes strong distortions at the Fe centre which as magnetic studies reveal prevent spin crossover trapping 1–4 in the HS state.


2017 ◽  
Vol 41 (13) ◽  
pp. 5904-5915 ◽  
Author(s):  
Lukáš Pogány ◽  
Ján Moncol ◽  
Ján Pavlik ◽  
Ivan Šalitroš

Utilization of 2-hydroxybenzophenone derivatives for the preparation of iron(iii) Schiff base complexes resulted in a series of high-spin, mostly antiferromagnetically coupled systems.


2017 ◽  
Vol 24 (20) ◽  
pp. 5191-5203 ◽  
Author(s):  
Lukáš Pogány ◽  
Barbora Brachňaková ◽  
Ján Moncol ◽  
Ján Pavlik ◽  
Ivan Nemec ◽  
...  

2014 ◽  
Vol 793 ◽  
pp. 77-83
Author(s):  
Azusa Muraoka ◽  
Kamel Boukheddaden

We performed of Monte Carlo simulations using Ising-like model on two-dimensional core/shell rectangular lattice L×2L for different sizes in order to study the effect of surface and size on the thermal behavior of spin-crossover nanoparticles. The surface effect is accounted for by constraining all the atoms situated in the boundary in the high-spin state as a result of the weak ligand-field prevailing in the coordination shell. This result is similar to square lattice of spin-crossover nanoparticles, and in agreement with experimental data. Such a non-trivial change is explained as due to the competition between the negative pressures induced the high spin state surface and the bulk properties. We also described the way in which the usual occurrence condition of the first-order transition has to be adapted to the nanoscale.


2002 ◽  
Vol 75 (7-8) ◽  
pp. 733-741 ◽  
Author(s):  
K. Boukheddaden ◽  
F. Varret ◽  
S. Salunke ◽  
J. Linares ◽  
E. Codjovi

2017 ◽  
Vol 46 (25) ◽  
pp. 8004-8008 ◽  
Author(s):  
Wang-Kang Han ◽  
Long-Fang Qin ◽  
Chun-Yan Pang ◽  
Cai-Kun Cheng ◽  
Wei Zhu ◽  
...  

A chiral iron(ii) complex with two polymorphs, one that undergoes a gradual spin crossover, whilst the other remains in a high-spin state but shows a typical ferroelectric feature, is reported.


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