%0 Journal Article
%A Milin, Eric
%A Belaïd, Sabrina
%A Patinec, Véronique
%A Triki, Smail
%A Chastanet, Guillaume
%A Marchivie, Mathieu
%D 2016
%T Dinuclear Spin-Crossover Complexes Based on Tetradentate
and Bridging Cyanocarbanion Ligands
%U https://acs.figshare.com/articles/journal_contribution/Dinuclear_Spin-Crossover_Complexes_Based_on_Tetradentate_and_Bridging_Cyanocarbanion_Ligands/3581535
%R 10.1021/acs.inorgchem.6b01542.s001
%2 https://ndownloader.figshare.com/files/5665785
%K OH
%K Bridging Cyanocarbanion Ligands Spin-crossover
%K Dinuclear Spin-Crossover Complexes
%K 2 exhibit SCO behaviors
%K χ m T product
%K dinuclear complexes 1
%K 1 D supramolecular structure
%K crystal structure determinations
%K tcpd
%K uncoordinated nitrile groups
%K Fe 2
%K CH
%K MeOH
%K centrosymmetrical dinuclear structure
%X Spin-crossover (SCO)
Fe(II) dinuclear complexes of formula [Fe2(tmpa)2(μ2-tcpd)2]·0.8(CH3OH)
(1·MeOH) and [Fe2(andmpa)2(μ2-tcpd)2]·2CH3OH (2·MeOH) (tmpa = tris(2-pyridylmethyl)amine, andmpa =
bis(2-pyridylmethyl)aminomethyl)aniline, (tcpd)2– = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide) have been synthesized
and characterized by infrared spectroscopy, X-ray diffraction, and
magnetic measurements. The crystal structure determinations of the
two complexes (1·MeOH and 2·MeOH) and the desolvated complex 1 (from 1·MeOH) revealed a neutral centrosymmetrical dinuclear structure in which
the (tcpd)2– cyanocarbanion acts as a double μ2-bridging ligand between two [FeL]2+ (L = tmpa
(1), andmpa (2)) units involving two free
coordination sites in the cis configuration. Examination
of the shortest intermolecular contacts in 1·MeOH and 1 reveals no significant hydrogen bonding between
the dinuclear units, while in 2·MeOH these units
are held together by significant hydrogen bonds between one of the
uncoordinated nitrile groups and the anilate function, giving rise
to 1D supramolecular structure. The three dinuclear complexes 1, 2·MeOH, and 2 exhibit SCO
behaviors which have been evidenced by the thermal evolutions of the
χmT product and by the average values
of the six Fe–N distances for 1 and 2·MeOH, that reveal a gradual conversion with transition temperatures (T1/2) at ca. 352 K (1), 196 K (2), and 180 K (2·MeOH). For the solvated 1·MeOH, the sharp SCO transition observed around 365
K was induced by the desolvatation process above 330 K during the
magnetic measurements.
%I ACS Publications