%0 Journal Article
%A Schmitz, Sebastian
%A Kovalchuk, Andrew
%A Martín-Rodríguez, Alejandro
%A Leusen, Jan van
%A Izarova, Natalya V.
%A Bourone, Svenja D. M.
%A Ai, Yong
%A Ruiz, Eliseo
%A Chiechi, Ryan C.
%A Kögerler, Paul
%A Monakhov, Kirill Yu.
%D 2018
%T Element-Selective Molecular Charge Transport Characteristics of Binuclear
Copper(II)-Lanthanide(III) Complexes
%U https://acs.figshare.com/articles/journal_contribution/Element-Selective_Molecular_Charge_Transport_Characteristics_of_Binuclear_Copper_II_-Lanthanide_III_Complexes/6856460
%R 10.1021/acs.inorgchem.8b01279.s001
%2 https://acs.figshare.com/ndownloader/files/12486809
%K thioether-Schiff base
%K isostructural dinuclear 3
%K Element-Selective Molecular Charge Transport Characteristics
%K Cu centers
%K Theoretical calculations
%K 2- hydroxy -3-methoxybenzaldehyde
%K antiferromagnetic exchange interactions
%K complexes 1
%K C 15 H 15
%K HL
%K Y 4
%K square-pyramidal coordination environment
%K electrodes show
%K Dy 3
%K lanthanide ion
%K Tb 2
%K Cu II
%K 4 points
%K Large-area electron transport studies
%K transmission spectra
%K electron transport
%K gold substrate
%K Ln
%K MeOH
%K copper ions
%K III
%K CuLn
%K -4f complexes
%K Gd 1
%K title compound 1
%X A series
of isostructural dinuclear 3d-4f complexes, isolated as [CuLn(L·SMe)2(OOCMe)2(NO3)]·xMeOH (Ln = Gd 1, Tb 2, Dy 3, and Y 4; x = 0.75–1) and comprising
one acetate and two thioether-Schiff base (L·SMe–) bridging ligands based on 4-(methylthio)aniline and 2-hydroxy-3-methoxybenzaldehyde
(HL·SMe = C15H15NO2S), was synthesized
and fully characterized. The magnetic properties of the charge-neutral
{CuLn} complexes are dominated by ferromagnetic CuII–LnIII exchange interactions. Large-area electron transport studies
reveal that the average conductivity of robust, self-assembled {CuLn}
monolayers on a gold substrate is significantly lower than that of
common alkanethiolates. Theoretical calculations of transmission spectra
of individual complexes 1 and 4 embedded
between two metallic electrodes show that the molecular current–voltage
(I–V) characteristics are
strongly influenced by electron transport through the Cu centers and
thus fully independent of the lanthanide ion, in excellent agreement
with the experimental I–V data for 1–4. The β-polarized
transmission indicated by calculations of 1 and 4 points out their potential as spin filters. In addition,
the reactivity of the title compound 1 with CuII in a square-pyramidal coordination environment toward methanolate
and azide was examined, resulting in the formation of a linear trinuclear
complex, [Cu2Na(L·SMe)4]NO3·3MeOH (5), characterized by antiferromagnetic
exchange interactions between the two copper ions.
%I ACS Publications