Search results for "Single ion"

A SIM-MOF: Three-Dimensional Organisation of Single-Ion Magnets with Anion-Exchange Capabilities

2014

The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single-ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM-MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)4](TfO)3⋅x solvent (Ln=Tb (1); Dy (2); Ho (3); Er (4); TfO=triflate), in which the lanthanoid centres have an square-antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In add…

Single-Ion Magnetic Behavior in CoII-CoIII Mixed-Valence Dinuclear and Pseudodinuclear Complexes

2017

Two CoII–CoIII mixed-valence complexes of molecularformulas [Co2(H2L)2(H2O)2][Co2(H2L)2(H2O)(m-phth)]·8(H2O) {1;H2L2–= 2-[(2-hydroxy-3-methoxybenzylidene)amino]-2-(hydroxymethyl)propane-1,3-diolato, m-phth = 1,3-benzene-dicarboxylate} and [Co4(H2L)4(H2O)2(ppda)]·2(dmf)·3.2(H2O) {2;ppda = 1,4-phenylenediacrylate; dmf = N,N-dimethyl-formamide} were synthesized and characterized by single-crys-tal X-ray diffraction and magnetic studies at low temperature.The structural determination reveals that 1 is composed of di-nuclear ion pairs, namely, a cationic [Co2(H2L)2(H2O)2]+(1+) andan anionic [Co2(H2L)2(H2O)(m-phth)]–(1–) unit. In each of these ions, the CoIIand CoIIIcenters present distorted octa…

{CoIIIMnIII}ncorrugated chains based on heteroleptic cyanido metalloligands

2015

The use of the cyanide-bearing complexes PPh4[CoIII(4,4′-dmbipy)(CN)4] and PPh4[CoII(dmphen)(CN)3] as metalloligands towards [Mn(salen)(H2O)]ClO4 affords one-dimensional coordination polymers with the formulas {[MnIII(salen)(μ-NC)2CoIII(4,4-dmbipy)(CN)2]·H2O}n (1) and {[MnIII(salen)(μ-NC)2CoIII(dmphen)(CN)2]}n (2) [PPh4+ = tetraphenylphosphonium cation, 4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine, dmphen = 2,9-dimethyl-1,10-phenanthroline and H2salen = N,N′-ethylenebis(salicylideneimine)]. Compounds 1 and 2 were structurally characterized. Their structures consist of neutral chains with regular alternating [Mn(salen)]+ and [CoIII(4,4′-dmbipy)(CN)4]− (1)/[CoIII(dmphen)(CN)4]− (2) moieties, t…

Cover Picture: Dynamic Magnetic and Optical Insight into a High Performance Pentagonal Bipyramidal DyIII Single-Ion Magnet (Chem. Eur. J. 24/2017)

2017

Single ion magnets based on lanthanoid polyoxomolybdate complexes

2016

Polyoxometalate (POM) chemistry has recently offered excellent examples of single ion magnets (SIMs) and molecular spin qubits. Compared with conventional coordination compounds, POMs provide rigid and highly symmetric coordination sites. However, all POM-based SIMs reported to date exhibit a very limited range of possibilities for chemical processability. We present herein two new families of POM-based SIMs which are soluble in organic solvents: [Ln(β-Mo8O26)2]5− {LnIII = Tb, Dy, Ho, Er, Tm and Yb} and the functionalised POMs [Ln{Mo5O13(OMe)4NNC6H4-p-NO2}2]3− {LnIII = Tb, Dy, Ho, Er, Yb and Nd}. In addition, these two families represent the first SIMs based on polyoxomolybdates. A magneto-…

Reversible solvatomagnetic switching in a single-ion magnet from an entatic state

2016

We have developed a new strategy for the design and synthesis of multifunctional molecular materials showing reversible magnetic and optical switching.

Dynamic Magnetic and Optical Insight into a High Performance Pentagonal Bipyramidal Dy(III) Single-Ion Magnet

2017

The pentagonal bipyramidal single-ion magnets (SIMs) are among the most attractive prototypes of high-performance single-molecule magnets (SMMs). Here, a fluorescence-active phosphine oxide ligand CyPh2PO (=cyclohexyl(diphenyl)phosphine oxide) was introduced into [Dy(CyPh2PO)2(H2O)5]Br3⋅2 (CyPh2PO)⋅EtOH⋅3 H2O, and combined dynamic magnetic measurement, optical characterization, ab initio calculation, and magneto-optical correlation of this high-performance pseudo-D5h DyIII SIM with large Ueff (508(2) K) and high magnetic hysteresis temperature (19 K) were performed. This work provides a deeper insight into the rational design of promising molecular magnets.

Single ion magnet behaviour in a two-dimensional network of dicyanamide-bridged cobalt(II) ions

2015

A novel two-dimensional coordination polymer of the formula [Co(dca)2(atz)2]n (1) resulted from assembling trans-bis(2-amino-1,3,5-triazine)cobalt(II) motifs by dicyanamide spacers. Variable-temperature dc and ac magnetic susceptibility measurements of 1 show that the high-spin cobalt(II) ions act as single ion magnets (SIMs).

Influence of Peripheral Substitution on the Magnetic Behavior of Single-Ion Magnets Based on Homo- and Heteroleptic TbIIIBis(phthalocyaninate)

2013

A series of homoleptic ([Tb(III)(Pc)(2) ]) and heteroleptic ([Tb(III)(Pc)(Pc')]) Tb(III) bis(phthalocyaninate) complexes that contain different peripheral substitution patterns (i.e., tert-butyl or tert-butylphenoxy groups) have been synthesized in their neutral radical forms and then reduced into their corresponding anionic forms as stable tetramethylammonium/tetrabutylammonium salts. All of these compounds were spectroscopically characterized and their magnetic susceptibility properties were investigated. As a general trend, the radical forms exhibited larger energy barriers for spin reversal than their corresponding reduced compounds. Remarkably, heteroleptic complexes that contain elect…

Modeling the magnetic properties of lanthanide complexes: relationship of the REC parameters with Pauling electronegativity and coordination number

2015

In a previous study, we introduced the Radial Effective Charge (REC) model to study the magnetic properties of lanthanide single ion magnets. Now, we perform an empirical determination of the effective charges (Zi) and radial displacements (Dr) of this model using spectroscopic data. This systematic study allows us to relate Dr and Zi with chemical factors such as the coordination number and the electronegativities of the metal and the donor atoms. This strategy is being used to drastically reduce the number of free parameters in the modeling of the magnetic and spectroscopic properties of f-element complexes. SPINMOL FP7-ERC-247384 ERC-CoG-647301 DECRESIM MAT2011-22785 MAT2014-56143-R CTQ2…