A Strongly Blue-Emitting Heptametallic [Dy^III₇] Centered-Octahedral Single-Molecule Magnet

The employment of 2-(β-naphthalideneamino)-2-(hydroxymethyl)-1-propanol and 2-aminoisobutyric acid in dysprosium chemistry has led to the isolation of a novel heptanuclear [DyIII7] cluster displaying single-molecule-magnetism behavior and blue-emitting properties

Employment of a New Tripodal Ligand for the Synthesis of Cobalt(II/III), Nickel(II), and Copper(II) Clusters: Magnetic, Optical, and Thermal Properties

The employment of 2-(β-naphthalideneamino)-2-(hydroxymethyl)-1-propanol (LH₃) in cobalt, nickel, and copper chemistry has led to the isolation of five new metallic complexes with interesting magnetic properties. More specifically, the reaction of Co­(OAc)₂·4H₂O with LH₃ in MeOH in the presence of NEt₃ under solvothermal conditions forms the complex [Co^III₂Co^II₃(L)₂(LH)₂(L′)­(OAc)]·8.5MeOH (<b>1</b>·8.5MeOH; L′ = monoanion of 2-hydroxy-1-naphthaldehyde), while in nickel chemistry, a similar reaction of Ni­(OAc)₂·6H₂O with LH₃ in MeCN in the presence of NEt₃ under high pressure/temperature forms the complex [Ni^II(LH₂)₂]·2MeCN (<b>2</b>·2MeCN). Repeating the same reaction in MeOH and switching from Ni­(OAc)₂·4H₂O to NiSO₄·4H₂O produces the complex [Ni^II₄(HL)₃(OMe)­(MeOH)₃]­(SO₄)_0.5·2MeOH (<b>3</b>·2MeOH) under solvothermal conditions. Furthermore, in copper chemistry, the reaction of Cu₂(OAc)₄·2H₂O with LH₃ in the presence of NEt₃ in MeOH under solvothermal conditions affords the complex [Cu^II₄(LH)₄] (<b>4</b>), while the same reaction under ambient temperature and pressure conditions forms [Cu^II₄(LH)₄] ·3.5MeOH·2.25H₂O (<b>5</b>·3.5MeOH·2.25H₂O). Complex <b>1</b> is a mixed-valent [Co^III₂Co^II₃] complex, consisting of three edge-sharing [Co₃] triangles. Complex <b>2</b> is a nickel­(II) monomer in which the central metal is found in an octahedral geometry, while complex <b>3</b> describes a [Ni^II₄] cubane. Complexes <b>4</b> and <b>5</b> may be considered as structural isomers because they possess the same formulas but different topologies: <b>4</b> describes a highly distorted [Cu^II₄(OR)₄]⁴⁺ eight-membered ring, while <b>5</b> consists of a distorted [Cu^II₄(μ₃-OR)₄]⁴⁺ cubane. In addition, <b>5</b> can be converted to <b>4</b> in excellent yield under solvothermal conditions. Direct-current magnetic susceptibility studies have been carried out in the 5–300 K range for complexes <b>1</b> and <b>3</b>–<b>5</b>, revealing the possibility of a high-spin ground state for <b>1</b>, an <i>S</i> = 4 ground state for <b>2</b>, and diamagnetic ground states for <b>4</b> and <b>5</b>

A Strongly Blue-Emitting Heptametallic [Dy^III₇] Centered-Octahedral Single-Molecule Magnet

The employment of 2-(β-naphthalideneamino)-2-(hydroxymethyl)-1-propanol and 2-aminoisobutyric acid in dysprosium chemistry has led to the isolation of a novel heptanuclear [Dy^III₇] cluster displaying single-molecule-magnetism behavior and blue-emitting properties

Employment of a New Tripodal Ligand for the Synthesis of Cobalt(II/III), Nickel(II), and Copper(II) Clusters: Magnetic, Optical, and Thermal Properties

The employment of 2-(β-naphthalideneamino)-2-(hydroxymethyl)-1-propanol (LH₃) in cobalt, nickel, and copper chemistry has led to the isolation of five new metallic complexes with interesting magnetic properties. More specifically, the reaction of Co­(OAc)₂·4H₂O with LH₃ in MeOH in the presence of NEt₃ under solvothermal conditions forms the complex [Co^III₂Co^II₃(L)₂(LH)₂(L′)­(OAc)]·8.5MeOH (<b>1</b>·8.5MeOH; L′ = monoanion of 2-hydroxy-1-naphthaldehyde), while in nickel chemistry, a similar reaction of Ni­(OAc)₂·6H₂O with LH₃ in MeCN in the presence of NEt₃ under high pressure/temperature forms the complex [Ni^II(LH₂)₂]·2MeCN (<b>2</b>·2MeCN). Repeating the same reaction in MeOH and switching from Ni­(OAc)₂·4H₂O to NiSO₄·4H₂O produces the complex [Ni^II₄(HL)₃(OMe)­(MeOH)₃]­(SO₄)_0.5·2MeOH (<b>3</b>·2MeOH) under solvothermal conditions. Furthermore, in copper chemistry, the reaction of Cu₂(OAc)₄·2H₂O with LH₃ in the presence of NEt₃ in MeOH under solvothermal conditions affords the complex [Cu^II₄(LH)₄] (<b>4</b>), while the same reaction under ambient temperature and pressure conditions forms [Cu^II₄(LH)₄] ·3.5MeOH·2.25H₂O (<b>5</b>·3.5MeOH·2.25H₂O). Complex <b>1</b> is a mixed-valent [Co^III₂Co^II₃] complex, consisting of three edge-sharing [Co₃] triangles. Complex <b>2</b> is a nickel­(II) monomer in which the central metal is found in an octahedral geometry, while complex <b>3</b> describes a [Ni^II₄] cubane. Complexes <b>4</b> and <b>5</b> may be considered as structural isomers because they possess the same formulas but different topologies: <b>4</b> describes a highly distorted [Cu^II₄(OR)₄]⁴⁺ eight-membered ring, while <b>5</b> consists of a distorted [Cu^II₄(μ₃-OR)₄]⁴⁺ cubane. In addition, <b>5</b> can be converted to <b>4</b> in excellent yield under solvothermal conditions. Direct-current magnetic susceptibility studies have been carried out in the 5–300 K range for complexes <b>1</b> and <b>3</b>–<b>5</b>, revealing the possibility of a high-spin ground state for <b>1</b>, an <i>S</i> = 4 ground state for <b>2</b>, and diamagnetic ground states for <b>4</b> and <b>5</b>

Enneanuclear [Ni₆Ln₃] Cages: [Ln^III₃] Triangles Capping [Ni^II₆] Trigonal Prisms Including a [Ni₆Dy₃] Single-Molecule Magnet

The use of (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) ligand, H₃L, in Ni/Ln chemistry has led to the isolation of three new isostructural [Ni^II₆Ln^III₃] metallic cages. More specifically, the reaction of Ni­(ClO₄)₂·6H₂O, the corresponding lanthanide nitrate salt, and H₃L in MeCN, under solvothermal conditions in the presence of NEt₃, led to the isolation of three complexes with the formulas [Ni₆Gd₃(OH)₆(HL)₆(NO₃)₃]·5.75MeCN·2Et₂O·1.5H₂O (<b>1</b>·5.75MeCN·2Et₂O·1.5H₂O), [Ni₆Dy₃(OH)₆(HL)₆(NO₃)₃]·2MeCN·2.7Et₂O·2.4H₂O (<b>2</b>·2MeCN·2.7Et₂O·2.4H₂O), and [Ni₆Er₃(OH)₆(HL)₆(NO₃)₃]·5.75MeCN·2Et₂O·1.5H₂O (<b>3</b>·5.75MeCN·2Et₂O·1.5H₂O). The structure of all three clusters describes a [Ln^III₃] triangle capping a [Ni^II₆] trigonal prism. Direct current magnetic susceptibility studies in the 5–300 K range for complexes <b>1</b>–<b>3</b> reveal the different nature of the magnetic interactions within the clusters: dominant antiferromagnetic exchange interactions for the Dy^III and Er^III analogues and dominant ferromagnetic interactions for the Gd^III example. Alternating current magnetic susceptibility measurements under zero external dc field displayed fully formed temperature- and frequency-dependent out-of-phase peaks for the [Ni^II₆Dy^III₃] analogue, establishing its single molecule magnetism behavior with <i>U</i>_eff = 24 K

Enneanuclear [Ni₆Ln₃] Cages: [Ln^III₃] Triangles Capping [Ni^II₆] Trigonal Prisms Including a [Ni₆Dy₃] Single-Molecule Magnet

The use of (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) ligand, H₃L, in Ni/Ln chemistry has led to the isolation of three new isostructural [Ni^II₆Ln^III₃] metallic cages. More specifically, the reaction of Ni­(ClO₄)₂·6H₂O, the corresponding lanthanide nitrate salt, and H₃L in MeCN, under solvothermal conditions in the presence of NEt₃, led to the isolation of three complexes with the formulas [Ni₆Gd₃(OH)₆(HL)₆(NO₃)₃]·5.75MeCN·2Et₂O·1.5H₂O (<b>1</b>·5.75MeCN·2Et₂O·1.5H₂O), [Ni₆Dy₃(OH)₆(HL)₆(NO₃)₃]·2MeCN·2.7Et₂O·2.4H₂O (<b>2</b>·2MeCN·2.7Et₂O·2.4H₂O), and [Ni₆Er₃(OH)₆(HL)₆(NO₃)₃]·5.75MeCN·2Et₂O·1.5H₂O (<b>3</b>·5.75MeCN·2Et₂O·1.5H₂O). The structure of all three clusters describes a [Ln^III₃] triangle capping a [Ni^II₆] trigonal prism. Direct current magnetic susceptibility studies in the 5–300 K range for complexes <b>1</b>–<b>3</b> reveal the different nature of the magnetic interactions within the clusters: dominant antiferromagnetic exchange interactions for the Dy^III and Er^III analogues and dominant ferromagnetic interactions for the Gd^III example. Alternating current magnetic susceptibility measurements under zero external dc field displayed fully formed temperature- and frequency-dependent out-of-phase peaks for the [Ni^II₆Dy^III₃] analogue, establishing its single molecule magnetism behavior with <i>U</i>_eff = 24 K