Pentacoordinate and Hexacoordinate Mn(III) Complexes of Tetradentate Schiff-Base Ligands Containing Tetracyanidoplatinate(II) Bridges and Revealing Uniaxial Magnetic Anisotropy

Abstract

(2b), where H 2 L4B = N,N'-benzene-bis(4-aminodiethylene-salicylideneiminate), consists of two [{Mn(L4B)} moieties, involving pentacoordinate Mn III atoms, bridged through the tetracyanidoplatinate (II) bridges to which they are coordinated in a trans fashion. Both complexes possess uniaxial type of magnetic anisotropy, with D (the axial parameter of zero-field splitting) = −3.7(1) in 2a and −2.2(1) cm −1 in 2b. Furthermore, the parameters of magnetic anisotropy 2a and 2b were also thoroughly studied by theoretical complete active space self-consistent field (CASSCF) methods, which revealed that the former is much more sensitive to the ligand field strength of the axial ligands.

Positive and Negative Two-Dimensional Thermal Expansion via Relaxation of Node Distortions

“…Single crystals of [Mn­(salen)] 2 [Pt­(CN) 4 ]·H 2 O ( 1·H 2 O ) were prepared by mixing methanol solutions of [Mn­(salen)]Cl and K 2 [Pt­(CN) 4 ]·3H 2 O in a 2:1 ratio. , At 150 K 1·H 2 O crystallizes in a tetragonal ( P 4/ ncc ). Undulating zigzag layers are constructed from two-connecting [Mn­(salen)] + units linked through the nitrogen atoms of the cyanide groups of four-connecting [Pt­(CN) 4 ] 2– units (Figure (a)).…”

Magnetic Anisotropy and Field‐induced Slow Relaxation of Magnetization in Tetracoordinate CoII Compound [Co(CH3‐im)2Cl2]

“…Nevertheless, if we consider a special category of SMMs with one paramagnetic center, so called single-ion magnets (SIMs), then the deliberate modulation of the magnetic anisotropy is easier and depends reasonably on the topology and donor atom constitution of the coordination polyhedron [ 2 ]. Up to now, several correlations on the relationship between a structure and anisotropy parameters have been reported, namely for tetracoordinate [ 8 , 9 ], pentacoordinate [ 10 , 11 ], hexacoordinate Ni II and Co II compounds [ 12 , 13 ], tetracoordinate Fe II compounds [ 14 ] and penta and hexacoordinate Mn III compounds [ 15 , 16 ]. From these, the largest number of complexes exhibiting slow-relaxation of magnetization belongs undoubtedly to the group of tetracoordinate Co II compounds, which we have chosen as an object of the present study.…”

Crystal structure of poly[tetra(μ 2-cyanido-κ2 N:O)-bis(N,N-dimethylformamide-κO)-manganese(II)-platinum(II)], C10H14MnN6O2Pt

“…The crystal structures of the related heterometallic cyanido-bridged Mn-Pt-complexes [{Mn(salen)} 2 Pt(CN) 4 ] n (salen = N,N′-bis(salicylidene)ethylenediiminato) [5,6], [Mn(L)Pt(CN) 4 ] n (L = 2,13-dimethyl-3,12-diaza-6,9-dioxa-1(2,6)-pyridinacyclotridecaphane-2,12-diene) [7] and [Mn(phen) Pt(CN) 4 ] n (phen = 1,10-phenanthroline) [8] have been determined previously.…”