A highly anisotropic family of hexagonal bipyramidal Dy(III) unsaturated 18-crown-6 complexes exceeding the blockade barrier over 2700 K: a computational exploration.

In the present work, we have explored a series of unsaturated hexa-18-crown-6 (U18C6) ligands towards designing highly anisotropic Dy(III) based single-ion magnets (SIMs) with the general formula [Dy(U18C6)X] (where U18C6 = [CHO] (1), [CHS] (2), [CHSe] (3), [CHOS] (4), [CHOSe] (5) and X = F, Cl, Br, I, OBu and OSiPh). By analysing the electronic structure, bonding and magnetic properties, we find that the U18C6 ligands prefer stabilising the highly symmetric eight-coordinated hexagonal bipyramidal geometry (HBPY-8), which is the source of the near-Ising type anisotropy in all the [Dy(U18C6)X] complexes. Moreover, the ability of sulfur/selenium substituted U18C6 ligands to stabilize the highly anisotropic HBPY-8 geometry makes them more promising towards engineering the equatorial ligand field compared to substituted saturated 18C6 ligands where the exodentate arrangement of the S lone pairs results in low symmetry.

Field induced single ion magnet behavior in Co complexes in a distorted square pyramidal geometry.

We report three Co-based complexes with the general formula [Co(L)(X)] by changing the halide/pseudo-halide ions [X = NCSe (1SeCN); Cl (2Cl) and Br (3Br)]. The obtained and values confirm a distorted square pyramidal geometry around the Co ion in all these complexes. In these three complexes, the central Co ion is situated above the basal plane of the square pyramidal geometry.

Understanding electrostatics and covalency effects in highly anisotropic organometallic sandwich dysprosium complexes [Dy(CR)] (where R = H, SiH, CH and = 4 to 9): a computational perspective.

In this article, we have thoroughly studied the electronic structure and 4f-ligand covalency of six mononuclear dysprosium organometallic sandwich complexes [Dy(CR)] (where R = H, SiH, CH; = 4 to 9; = 1, 3) using both the scalar relativistic density functional and complete active space self-consistent field (CASSCF) and N-electron valence perturbation theory (NEVPT2) method to shed light on the ligand field effects in fine-tuning the magnetic anisotropy of these complexes. Energy decomposition analysis (EDA) and -based ligand field theory AILFT calculations predict the sizable 4f-ligand covalency in all these complexes. The analysis of CASSCF/NEVPT2 computed spin-Hamiltonian (SH) parameters indicates the stabilization of |±15/2〉 for [Dy(C(SiH))] (1), [Dy(C(CH))] (2) and [Dy(CH)] (3) complexes with the value of 1867.

Ru(II)/Ru(IV)-catalyzed C(sp)-H allylation with alkene difunctionalization to access isochroman-1-imines.

Merging C(sp)-H allylation and alkene difunctionalization events to access isochroman-1-imines, using -aroyl aminoesters, MBH acetates, and NBS, under Ru(II)/Ru(IV) catalysis has been developed. Using H NMR, ESI-MS, HRMS, control reactions, deuterium labeling experiments, and DFT analysis, the allyl transfer (redox) process was proven to involve in C-H allylation rather than olefin insertion. Scale-up and synthetic transformations demonstrated the sustainability of this method.

A porous cobalt(II)-organic framework exhibiting high room temperature proton conductivity and field-induced slow magnetic relaxation.

A two-dimensional (2D) cobalt(II) metal-organic framework (MOF) constructed by a ditopic organic ligand, formulated as {[Co(Hbic)(HO)]·4HO} (1) (Hbic = 1-benzimidazole-5-carboxylic acid), was hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction shows that the distorted octahedral Co ions, as coordination nodes, are bridged to form 2D honeycomb networks, which are further organized into a 3D supramolecular porous framework through multiple hydrogen bonds and interlayer π-π interactions. Dynamic crystallography experiments reveal the anisotropic thermal expansion behavior of the lattice, suggesting a flexible hydrogen-bonded 3D framework.

Exchange-driven slow relaxation of magnetization in NiII2LnIII2 (Ln = Y, Gd, Tb and Dy) butterfly complexes: experimental and theoretical studies.

The tetranuclear NiII2LnIII2 complexes, [{L'{Ni(MeOH)(μ-OAc)}(μ-MeO)Ln}, Ln = Y (1), Gd (2), Tb (3), and Dy (4)], were prepared using a Schiff base ligand, HL [HL = 3-{(2-hydroxy-3-methoxybenzylidene)amino}-2-(2-hydroxy-3-methoxyphenyl)-2,3-dihydroquinazolin-4(1)-one, where {L'} is the deprotonated open structure of HL]. X-ray crystallographic analysis of 1-4 revealed that all the complexes crystallized in the orthorhombic () space group, and possessed an isostructural tetranuclear butterfly or defect dicubane like core. Direct current magnetic susceptibility measurements performed on 2-4 revealed that all these complexes show an intramolecular ferromagnetic exchange coupling.

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

Precise control of the structures and magnetic properties of a molecular material constitutes an important challenge to realize tailor-made magnetic function. Herein, we report that the ligand-directed coordination self-assembly of a dianionic cobalt(II) mononuclear complex and selective organic linkers has led to two distinct dicobalt(II) complexes, [Co(pdms)(bpym)]·2MeCN (1) and [Co(pdms)(bipm)]·3DMF (2) (Hpdms = 1,2-bis(methanesulfonamide)benzene; bpym = 2,2'-bipyrimidine; bimp = 1,4-bis[(1-imidazol-1-yl)methyl]benzene). Structural analyses revealed that complexes 1 and 2 are discrete binuclear molecules containing two neutral {Co(pdms)} species bridged by bpym and bimp ligands, respectively, forming an exchange-coupled CoII2 dimer and a rare CoII2 metallocycle.

A Nd6 molecular butterfly: a unique all-in-one material for SMM, MCE and maiden photosensitized opto-electronic device fabrication.

Besides iron, ironically neodymium (Nd) is the most ubiquitously used metal for magnetic purposes, even among the lanthanides, when it comes to the field of molecular magnetism, yet it ranks among the least studied metals. However, strong apathy towards this magnetic lanthanide means that vital information will be missed, which is required for the advancement of the subject. Herein, we have successfully demonstrated the usefulness of a hexanuclear neodymium complex as a magnetic material, and also in electronic device fabrication.

Tuning the structure and magnetic properties distinct pyridine derivatives in cobalt(II) coordination polymers.

Precise modulation of the structure and magnetic properties of coordination compounds is of great importance in the development of framework magnetic materials. Herein, we report that the coordination self-assembly of a neutral cobalt(II) magnetic building block and selective pyridine derivatives as organic linkers has led to two distinct cobalt(II) coordination polymers, {Co(DClQ)(bpy)} (1) and {Co(DClQ)(tpb)} (2) (DClQ = (5,7-dichloro-8-hydroxyquinoline; bpy = 4, 4'-dipyridine; tpb = 1,2,4,5-tetra(4-pyridyl)benzene)). Structural analyses revealed that 1 and 2 are one-dimensional (1D) and 2D coordination polymers containing the same neutral magnetic building block [Co(DClQ)] bridged by bitopic bpy and tetratopic tpb ligands, respectively.