Synthesis, Crystal Structures and Magnetic Properties of Trinuclear {Ni2Ln} (LnIII = Dy, Ho) and {Ni2Y} Complexes with Schiff Base Ligands

The reaction of the Schiff base ligand o-OH-C6H4-CH=N-C(CH2OH)3, H4L, with Ni(O2CMe)2∙4H2O and lanthanide nitrate salts in a 4:2:1 ratio lead to the formation of the trinuclear complexes [Ni2Ln(H3L)4(O2CMe)2](NO3) (Ln = Dy (1), Ho (2), and Y (3)) which crystallize in the non-centrosymmetric space group Pna21. The complex cation consists of the three metal ions in an almost linear arrangement. The {Ni2Ln} moieties are bridged through two deprotonated Ophenolato groups from two different ligands. Each terminal NiII ion is bound to two ligands through their Ophenolato, the Nimino atoms and one of the protonated Oalkoxo groups in a distorted octahedral. The central lanthanide ion is coordinated to four Ophenolato oxygen from the four ligands, and four Ocarboxylato atoms from two acetates which are bound in the bidentate chelate mode, and the coordination polyhedron is biaugmented trigonal prism, which probably results in a non-centrosymmetric arrangement of the complexes in the lattice. The magnetic properties of 1–3 were studied and showed that 1 exhibits field induced slow magnetic relaxation.

1D iron(II)-1,2,4-triazolic chains with spin crossover assembled from discrete trinuclear complexes

We report on a molecular cationic iron(II) complex with a 4-amino-1,2,4-triazole ligand and a tetraiodomercurate anion exhibiting an incomplete spin crossover (SCO). The complex exhibits an unusual disordered structure with...

The Influence of Aryl Substituents on the Supramolecular Structures and Photoluminescence of Cyclic Trinuclear Pyrazolato Copper(I) Complexes

Cyclic trinuclear complexes with group 11 metal (I) ions are fascinating and important to coordination chemistry. One of the ligands known to form these cyclic trinuclear complexes is pyrazolate, which is a bridging ligand that coordinates many transition metal ions in a Npz–M–Npz linear mode (Npz = pyrazolyl nitrogen atom). In these group 11 metal (I) ions, copper is the most abundant metal. Therefore, polynuclear Copper(I) complexes are very important in this field. The cyclic trinuclear Copper(I) complex [Cu(3,5-Ph2pz)]3 (3,5-Ph2pz– = 3,5-diphenyl-1-pyrazolate anion) was reported in 1988 as a landmark complex, but its photoluminescence properties have hitherto not been described. In this study, we report the photoluminescence and two different polymorphs of [Cu(3,5-Ph2pz)]3 and its derivative [Cu(3-Me-5-Phpz)]3 (3-Me-5-Phpz– = 3-metyl-5-phenyl-1-pyrazale anion). The substituents in [Cu(3-Me-5-Phpz)]3 cause smaller distortions in the solid-state structure and a red-shift in photoluminescence due to the presence of intermolecular cuprophilic interactions.

Cadmium-Inspired Self-Polymerization of {LnIIICd2} Units: Structure, Magnetic and Photoluminescent Properties of Novel Trimethylacetate 1D-Polymers (Ln = Sm, Eu, Tb, Dy, Ho, Er, Yb)

A series of heterometallic carboxylate 1D polymers of the general formula [LnIIICd2(piv)7(H2O)2]n·nMeCN (LnIII = Sm (1), Eu (2), Tb (3), Dy (4), Ho (5), Er (6), Yb (7); piv = anion of trimethylacetic acid) was synthesized and structurally characterized. The use of CdII instead of ZnII under similar synthetic conditions resulted in the formation of 1D polymers, in contrast to molecular trinuclear complexes with LnIIIZn2 cores. All complexes 1–7 are isostructural. The luminescent emission and excitation spectra for 2–4 have been studied, the luminescence decay kinetics for 2 and 3 was measured. Magnetic properties of the complexes 3–5 and 7 have been studied; 4 and 7 exhibited the properties of field-induced single-molecule magnets in an applied external magnetic field. Magnetic properties of 4 and 7 were modelled using results of SA-CASSCF/SO-RASSI calculations and SINGLE_ANISO procedure. Based on the analysis of the magnetization relaxation and the results of ab initio calculations, it was found that relaxation in 4 predominantly occurred by the sum of the Raman and QTM mechanisms, and by the sum of the direct and Raman mechanisms in the case of 7.

Synthesis, Crystal Structures, Electronic Spectra, and Magnetic Properties of Thiolato-Bridged Trinuclear Cobalt(II) Complexes with N, N, S-Tridentate Thiolate Ligands

New trinuclear CoII complexes, [{Co(apaet)2}2Co]X2 (apaet– = 2-[(3-aminopropyl)amino]ethanethiolato; X = SCN (1), ClO4 (2), NO3 (3), Cl (4), Br (5), I (6)) and [{Co(apampt)2}2Co]X2 (apampt– = 1-[(3-aminopropyl)amino]-2-methylpropane-2-thiolato; X = NO3(7), ClO4 (8), Cl (9), Br (10), I (11)), and mononuclear CoIII complexes, [Co(apaet)2]X (X = ClO4 (12), NO3 (13)), were synthesized. Single-crystal X-ray crystallography of 1 and 7 confirmed that the trinuclear complexes have a linear arrangement of octahedral CoIIS2N4-tetrahedral CoIIS4-octahedral CoIIS2N4 chromophores where two thiolate ligands are coordinated to each terminal Co atom in a mer coordination mode and the two thiolato S atoms are further bound to the central Co atom, which is consistent with the electronic spectra and antiferromagnetic properties

Nickel(II) Salicylaldiminates: Re-Visiting a Classic

A series of Ni(II) trinuclear complexes, [Ni₃(sala-X)₆] (sala-X = <i>o</i>-[(<i>p</i>-X-phenylimino)methyl]phenol; X = Br <b>1-Br</b>, Me <b>1-Me</b> and OMe <b>1-OMe</b>), have been prepared and fully characterised. X-ray crystallographic studies reveal that the complexes are composed of <a>three face-sharing octahedral Ni(II) metal ions bridged by the phenoxide oxygens of the sala-X ligands</a>. Magnetic studies indicate that the magnetic Ni(II) centres are ferromagnetically coupled with the substituent group having only a minor impact on the magnitude of coupling. DFT calculations also support ferromagnetic coupling with smaller Ni-O-Ni angles leading to slightly larger coupling constants in line with previous studies.

Nickel(II) Salicylaldiminates: Re-Visiting a Classic

A series of Ni(II) trinuclear complexes, [Ni₃(sala-X)₆] (sala-X = <i>o</i>-[(<i>p</i>-X-phenylimino)methyl]phenol; X = Br <b>1-Br</b>, Me <b>1-Me</b> and OMe <b>1-OMe</b>), have been prepared and fully characterised. X-ray crystallographic studies reveal that the complexes are composed of <a>three face-sharing octahedral Ni(II) metal ions bridged by the phenoxide oxygens of the sala-X ligands</a>. Magnetic studies indicate that the magnetic Ni(II) centres are ferromagnetically coupled with the substituent group having only a minor impact on the magnitude of coupling. DFT calculations also support ferromagnetic coupling with smaller Ni-O-Ni angles leading to slightly larger coupling constants in line with previous studies.

Coordination Methods of Thioligands in Trinuclear Complexes of Platinum (II)

The trinuclear complexes with simple and mixed ligands of platinum (II) with mercaptoethanol and mercaptoethylamine have been generated and their contents and structures investigated by numerous physicochemical methods. Mercaptoethanol (SHCH2CH2OH) is coordinated monodentally with just sulfur atom and forms pentacyclic metalchelate ring, where as mercaptoethylamine (HSCH2CH2NH2) is coordinated monodentally as well as bidentally and forms an identical ring (pentacyclic metalchelate). The sulfur atom of ligands plays a bridge role between the metals in the trinuclear platinum complexes. The hydroxyl group of mercaptoethanol does not participate in the coordination