A new molecular conductor of (TMTSF)5[Dy(NCS)4(NO3)2]CHCl3 was prepared using the electrochemical oxidation method. The complex crystallizes in the Cmc21 (36) space group, where the partially-oxidized TMTSF molecules form a 1D (one-dimensional) column structure. The crystal shows a semiconducting behavior with a room temperature conductivity of 0.2 S·cm−1 and an activation energy of 34 meV at ambient pressure.
New three-dimensional (3D) lanthanide framework compounds supported by bridging thiocyanate ligand and K+ cations, K4[Ln(NCS)4(H2O)4](NCS)3(H2O)2(1: Ln = Dy, 2: Ln = Tb, 3: Ln = Gd) have been synthesized. A single-crystal X-ray diffraction study showed that all three compounds were isostructural and crystallized in the I 2/a space group. The K+ ion form 2D layers with thiocyanates which are further linked by [Ln(NCS)4(H2O)4]- complexes and additional thiocyanate ions to generate an interesting 3D framework structure. Compound 1 shows slow magnetic relaxation behavior under a zero direct current (DC) field, indicating that 1 behaves as a single-ion magnet (SIM). As estimated from AC magnetic measurements, the effective energy barrier for spin reversal in 1 was Ueff = 42 cm–1. Slow relaxation of magnetization under a small external DC field was also detected for 2 and 3 at 1.8 K.
Assembling
conductive or magnetic heterostructures by bulk inorganic
materials is important for making functional electronic or spintronic
devices, such as semiconductive p-doped and n-doped silicon for P–N
junction diodes, alternating ferromagnetic and nonmagnetic conductive
layers used in giant magnetoresistance (GMR). Nonetheless, there have
been few demonstrations of conductive or magnetic heterostructures
made by discrete molecules. It is of fundamental interest to prepare
and investigate heterostructures based on molecular conductors or
molecular magnets, such as single-molecule magnets (SMMs). Herein,
we demonstrate the fabrication of a series of molecular heterostructures
composed of (TTF)2M(pdms)2 (TTF = tetrathiafulvalene,
M = Co(II), Zn(II), Ni(II), H2pdms = 1,2-bis(methanesulfonamido)benzene)
multiple building blocks through a well-controlled step-by-step electrocrystallization
growth process, where the Co(pdms)2, Ni(pdms)2, and Zn(pdms)2 anionic complex is a SMM, paramagnetic,
and diamagnetic molecule, respectively. Magnetic and SMM properties
of the heterostructures were characterized and compared to the parentage
(TTF)2Co(pdms)2 complex. This study presents
the first methodology for creating molecule-based magnetic heterostructural
systems by electrocrystallization.
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