An Organic–Inorganic Hybrid Exhibiting Electrical Conduction and Single‐Ion Magnetism

Abstract

The first three-dimensional (3D) conductive single-ion magnet (SIM), (TTF)2[Co(pdms)2] (TTF = tetrathiafulvalene and H2pdms = 1,2-bis(methanesulfonamido)benzene), was electrochemically synthesized and investigated structurally, physically and theoretically. The quite close oxidation potential between neutral TTF and the coordination precursor, (HNEt3)2[M(pdms)2] (M = Co, Zn) causes multiple charge transfers (CTs) between SIM donor [M(pdms)2] nand the TTF •+ acceptor as well as an intra-donor CT from the pdms ligand to Co ion upon electrocrystallization. Usually TTF works as a donor, whereas in our system, TTF works as both a donor and an accepter due to the close oxidation potentials. Furthermore, the [M(pdms)2] ndonor and TTF •+ acceptor are not segregated but strongly interact with each other, contrary to reported layered donor-acceptor electrical conductors. The strong intermolecular and intramolecular interactions, combined with the CT, cause relatively 2 high electrical conductivity to very low temperature. Furthermore, SIM behaviour with slow magnetic relaxation and opening of hysteresis loops were observed. (TTF)2[Co(pdms)2] (2-Co) is an excellent building block for preparing new conductive SIM.

Electro‐Conductive Single‐Molecule Magnet Composed of a Dysprosium(III)‐Phthalocyaninato Double‐Decker Complex with Magnetoresistance

“…In other words, although this complex is bifunctional, the conduction properties and the SMM properties are not observed at the same time. There are only a few recent examples exhibiting bifunctionality in the same temperature range [10] . In order to solve this problem, there has been a demand for conductive SMMs that have high conductivities even at low‐temperature and high T B [10] .…”

Simultaneous manifestation of metallic conductivity and single-molecule magnetism in a layered molecule-based compound

“…Recently, our group has reported (TTF) 2 [Co(pdms) 2 ], which behaves as a semiconductor and an SMM in the same temperature region. 13 Due to its unusual mixed stacking structure, strong charge transfer between TTF and [Co(pdms) 2 ] affords electrical conduction down to 2 K with SMM properties up to 5 K, however, it is not metallic.…”

“…1b). [Co(pdms) 2 ] 2À is an outstanding SMM with a large negative zero-eld splitting D value (D ¼ À115 cm À1 ), 13 which is necessary for high energy barrier SMMs. The low energy absorbance band at 1200 nm (calculated at 960 nm by the TD-CAM-B3LYP method) corresponds to the electron transition from the 4 B 1 orbital to the 4 E orbital of the cobalt ion ( Fig.…”

Electro‐Conductive Single‐Molecule Magnet Composed of a Dysprosium(III)‐Phthalocyaninato Double‐Decker Complex with Magnetoresistance

“…There are only a few recent examples exhibiting bifunctionality in the same temperature range. [10] In order to solve this problem, there has been a demand for conductive SMMs that have high conductivities even at low-temperature and high T B . [10] In order to overcome this, supramolecular materials where SMMs have been attached to the outside of carbon nanotubes (CNTs) have been synthesized.…”

“…[10] In order to solve this problem, there has been a demand for conductive SMMs that have high conductivities even at low-temperature and high T B . [10] In order to overcome this, supramolecular materials where SMMs have been attached to the outside of carbon nanotubes (CNTs) have been synthesized. [11] However, the orientation of the guest SMM on the CNT surface has not been determined, and a correlation occurs only at an extremely low-temperature of 40 mK.…”