Spin crossover Fe(II) complexes of a cross-bridged cyclam derivative
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F18%3A73591080" target="_blank" >RIV/61989592:15310/18:73591080 - isvavai.cz</a>
Result on the web
<a href="https://pubs.rsc.org/en/content/articlepdf/2018/dt/c8dt00414e" target="_blank" >https://pubs.rsc.org/en/content/articlepdf/2018/dt/c8dt00414e</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/c8dt00414e" target="_blank" >10.1039/c8dt00414e</a>
Alternative languages
Result language
angličtina
Original language name
Spin crossover Fe(II) complexes of a cross-bridged cyclam derivative
Original language description
A cross-bridged cyclam derivative containing two 2-pyridylmethyl pendant arms (L = 4,11-bis((pyridin-2-yl)methyl)-1,4,8,11-tetraaza-bicyclo[6.6.2]hexadecane) was synthesized by dialkylation of the cross-bridged cyclam with 2-chloromethylpyridine. A series of Fe(ii) complexes with L and different counter anions of the formulas [Fe(L)][FeCl4 center dot H2O (1-H2O), [Fe(L)Cl-2.4H(2)O (2.4H(2)O), [Fe(L)](BF4)(2)center dot 0.5CH(3)CN (3.0.5CH(3)CN) and [Fe(L)](BPh4)(2)center dot CH3OH (4 center dot CH3OH) was prepared and thoroughly characterized. In all the cases, the [Fe(L)]2 cation adopts a cis-V configuration with a distorted octahedral geometry, and with the FeN6 donor set. The magnetic measurements within the temperature interval of 5-400 K revealed the spin crossover (SCO) behaviour of all the complexes with the transition temperature T-1/2 increasing with the counter anion in the order BF4- (3) < [FeCl4](2-) (1) < BPh4- (4). However, the SCO process was complete in the case of compound 3 only, with T1/2 = 177 K, which proceeded after removal of co-crystallized CH3CN molecules accompanied by a change of the crystallographic phase. The SCO behaviour of 3 was also confirmed by a single crystal X-ray analysis providing the average (Fe N)distances of 2.086 angstrom at 120 K and 2.197 angstrom at 293 K typical of low-spin, and high-spin Fe-II complexes, respectively. The obtained results clearly showed that the nature of the counter anion and the presence/absence of co-crystallized solvent molecule(s) significantly affected the temperature as well as the abruptness of the spin transition. This is the first report of SCO behaviour observed for iron complexes containing a cross-bridged cyclam derivative.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
DALTON TRANSACTIONS
ISSN
1477-9226
e-ISSN
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Volume of the periodical
47
Issue of the periodical within the volume
17
Country of publishing house
GB - UNITED KINGDOM
Number of pages
12
Pages from-to
6134-6145
UT code for WoS article
000431816000031
EID of the result in the Scopus database
2-s2.0-85046291871