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

Abstract

Single-molecule magnets (SMMs) show superparamagnetic behaviour below blocking temperature at the molecular scale, so they exhibit large magnetic density compared to the conventional magnets. Combining SMMs and molecular conductors in...

Field-induced slow magnetic relaxation behaviours in binuclear cobalt(ii) metallocycles and exchange-coupled clusters

“…20 In fact, as one the most studied mononuclear cobalt systems, the magneto-structural correlations on the distorted tetrahedral mononuclear cobalt complexes have been well studied experimentally and computationally. 20,[35][36][37][38][39][40][41][54][55][56] Generally, a smaller N-Co-N bite angle will result in a larger zero-field splitting. One of the recent studies revealed the significant non-linear dependency of the d-orbital splitting on the N-Co-N bite angle.…”

“…33,34 Following these lines, we further turned our attention to a tetrahedral mononuclear complex (HNEt 3 ) 2 [Co ( pdms) 2 ] (H 2 pdms = 1,2-bis(methanesulfonamide)benzene, Scheme 1), which possesses the highest reported effective energy barrier (213 cm −1 ) among the air-stable transitionmetal SIMs. 20 Then, this complex has been used as a great magnetic building unit for the development of novel magnetic conductors [35][36][37] and as a molecular model for theoretical investigation, 38,39 and inspired the construction of a radicalbridged dimeric Co II SMM 40 and similar Co II SIMs. 41 Encouraged by these interesting works, herein we found that the dianionic mononuclear complex [Co( pdms) 2 ] 2− is liable to form the stable neutral [Co( pdms)] species in the presence of nitrogen-containing organic ligands.…”

4f−π Molecular Hybrid Exhibiting Rich Conductive Phases and Slow Relaxation of Magnetization

“…Due to the high number of spins in the ground state and strong uniaxial magnetic moments, lanthanoid-based SMMs have been shown to display high performances, such as high energy barriers ( U ) and long relaxation times (τ). − Our group has focused on the cooperation of SMMs and electrical conductivities (σ) in one system, that is, a new class of nanomaterials called conductive SMMs, by using SMMs and organic conductors, such as bis­(ethylenedithio)­tetrathiafulvalene (BEDT-TTF, abbreviated as ET) and bis­(ethylenedioxy)­tetrathiafulvalene (BEDO-TTF, or BO). Yagubskii et al and our group have independently reported several conductive SMMs with Re 4+ , Mn 2+/3+ , and Co 2+ transition metal ions and ET, BO, and M­(dmit) 2 conductors (dmit = 4,5-dimercapto-1,3-dithiole-2-dithione), some of which exhibit metallic SMM properties in the same temperature range. − However, in comparison to transition metal-based SMMs, there are few reports on 4f-based conductive SMMs. We first reported the electrocrystallization of a Dy 3+ -based magnetic chain and ET molecules to afford semiconductive SMM compounds .…”

New Radical Cation Salts Based on BDH-TTP Donor: Two Stable Molecular Metals with a Magnetic [ReF6]2− Anion and a Semiconductor with a [ReO4]− Anion

“…As a result, the first conductive field-induced SMM was synthesized-(BEDO) 4[ReF6]•6H2O-in which conductivity and single-molecule magnetism coexist in the same temperature range [16]. More recently, another BEDO salt has been synthesized with a monomolecular magnet [Co(pdms)] 2-as a counterion, which also shows the coexistence of conductivity and monomolecular magnetism up to 11 K [17].…”