New Mixed‐Metal Aggregates Derived From Dinickel Complexes on a 2‐Formylphenolate Template: Counteranion Dependent Formation of 1D Chain and Discrete NaNi<sub>2</sub> Complexes

Paital, Alok Ranjan; Mikuriya, Masahiro; Ray, Debashis

doi:10.1002/ejic.200700694

Cited by 15 publications

(8 citation statements)

References 48 publications

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“…The 3 A 2g (F) → 3 T 2g (F) transition that usually appears above 700 nm is systematically missing for all three complexes . The absorptions at 372 nm (ε = 8184 L mol –1 cm –1 ), 405 nm (ε = 9743 L mol –1 cm –1 ), and 400 nm (ε = 2389 L mol –1 cm –1 ) correspond to the 3 A 2g (F) → 3 T 1g (P) transitions for the three complexes, respectively . The intense absorptions below 300 nm at 254 nm (ε = 39273 L mol –1 cm –1 ), 246 nm (ε = 27613 L mol –1 cm –1 ), and 258 nm (ε = 61561 L mol –1 cm –1 ) are the result of Ni II -bound ligand-based absorptions.…”

Section: Resultsmentioning

confidence: 97%

A New Family of Ni₄ and Ni₆ Aggregates from the Self-Assembly of [Ni₂] Building Units: Role of Carboxylate and Carbonate Bridges

et al. 2015

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Carboxylato (R = (t)Bu and Et) and carbonato bridges have been utilized for nickel(II)-based aggregates [Ni4(μ-H2L)2(μ3-OH)2(μ1,3-O2CBu(t))2](NO3)2·H2O·2DMF (1·H2O·2DMF), Ni4(μ-(hy)HL)2(μ3-OMe)2(μ1,1-N3)2(μ1,3-O2CEt)2]·4H2O (2·4H2O), and Ni6(μ4-L)(μ3-L)2(μ6-CO3)(H2O)8](ClO4)·9H2O (3·9H2O). Building blocks [Ni2(μ-H2L)](3+), [Ni2(μ-(hy)HL)](3+), and [Ni2(μ-L)](+) originating from [Ni2(μ-H2L)](3+) have been trapped in these complexes. The complexes have been characterized by X-ray crystallography, magnetic measurements, and density functional theory (DFT) analysis. In 1, the magnetic interactions are transmitted through the μ3-phenoxido/μ3-hydroxido/syn-syn-(t)BuCO2(-), μ3-phenoxido/μ3- hydroxido, and double μ3-phenoxido/double μ3-hydroxido bridges with J = +11.4 cm(-1), J1 = -2.1 cm(-1), and J2 = -2.8 cm(-1), respectively. In 2, the interactions are ferromagnetic, with J1 = +27.5 cm(-1), J2 = +20.62 cm(-1), and J3 = +1.52 cm(-1) describing the magnetic couplings through the μ-phenoxidoo/μ3-methoxido, μ-azido/μ3-methoxido, and μ3-methoxido/μ3-methoxido exchange pathways, respectively. Complex 3 gives J1 = -3.30 cm(-1), J2 = +1.7 cm(-1), and J3 = -12.8 cm(-1) for exchange pathways mediated by μ-phenoxido/μ-carbonato, μ-alkoxido/μ-alkooxido/μ-syn-syn-carbonato, and the μ-phenoxido/μ-carbonato, respectively. Interestingly, 1 and 3 below 20 K and 35 K, respectively, show an abrupt increase of the χMT product to reach a magnetic-field-dependent maximum, which is associated with a slightly frequency-dependent out-of-phase alternating-current peak. DFT calculations have also been performed on 1-3 to explain the exchange interaction mechanisms and to support the magnitude and sign of the magnetic coupling constants between the Ni(II) ions.

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Section: Resultsmentioning

confidence: 97%

A New Family of Ni₄ and Ni₆ Aggregates from the Self-Assembly of [Ni₂] Building Units: Role of Carboxylate and Carbonate Bridges

et al. 2015

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“…This difference agrees with the higher 2 J value found in compound 1 (a higher angle gives rise to a higher antiferromagnetic coupling) since the magnetic coupling for doubly oxo-bridged Ni(II) complexes is expected to become more antiferromagnetic as the angle deviates from 90° . A search in the CCDC database shows 12 similar Ni dimers with a N 2 O 2 coordination environment around each Ni atom and a double oxo bridge . Unfortunately, only one of these 12 Ni dimers reported to date has been magnetically characterized .…”

Section: Resultsmentioning

confidence: 97%

(Ni₂), (Ni₃), and (Ni₂+ Ni₃): A Unique Example of Isolated and Cocrystallized Ni₂and Ni₃Complexes

et al. 2009

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Structural and magnetic characterization of compound {[Ni(2)(L)(2)(OAc)(2)][Ni(3)(L)(2)(OAc)(4)]}.2CH(3)CN (3) (HL = the tridentate Schiff base ligand, 2-[(3-methylamino-propylimino)-methyl]-phenol) shows that it is a rare example of a crystal incorporating a dinuclear Ni(II) compound, [Ni(2)(L)(2)(OAc)(2)], and a trinuclear one, [Ni(3)(L)(2)(OAc)(4)]. Even more unusual is the fact that both Ni(II) complexes, [Ni(2)(L)(2)(OAc)(2)] (1) and [Ni(3)(L)(2)(OAc)(4)(H(2)O)(2)].CH(2)Cl(2).2CH(3)OH (2), have also been isolated and structurally and magnetically characterized. The structural analysis reveals that the dimeric complexes [Ni(2)(L)(2)(OAc)(2)] in cocrystal 3 and in compound 1 are almost identical-in both complexes, the Ni(II) ions possess a distorted octahedral geometry formed by the chelating tridentate ligand (L), a chelating acetate ion, and a bridging phenoxo group with very similar bond angles and distances. On the other hand, compound 2 and the trinuclear complex in the cocrystal 3 show a similar linear centrosymmetric structure with the tridentate ligand coordinated to the terminal Ni(II) and linked to the central Ni(II) by phenoxo and carboxylate bridges. The only difference is that a water molecule found in 2 is not present in the trinuclear unit of complex 3; instead, the coordination sphere is completed by an additional bridging oxygen atom from an acetate ligand. Variable-temperature (2-300 K) magnetic susceptibility measurements show that the dinuclear unit is antiferromagnetically coupled in both compounds (2J = -36.18 and -29.5 cm(-1) in 1 and 3, respectively), whereas the trinuclear unit shows a very weak ferromagnetic coupling in compound 3 (2J = 0.23 cm(-1)) and a weak antiferromagnetic coupling in 2 (2J = -8.7(2) cm(-1)) due to the minor changes in the coordination sphere.

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“…The lower energy 3 A 2g (F) → 3 T 2g (F) transition was not observed in the accessible wavelength range . The 3 A 2g (F) → 3 T 1g (P) transition appears at 371 nm (ε = 1289 L mol –1 cm –1 ), 373 nm (ε = 1476 L mol –1 cm –1 ) and 370 nm (ε = 8563 L mol –1 cm –1 ) for 1 , 2 and 3 , respectively . The intense absorptions at 258 (ε = 51237 L mol –1 cm –1 ), 259 (ε = 70737 L mol –1 cm –1 ), and 261 nm (ε = 169120 L mol –1 cm –1 ) are because of ligand-centered π → π* transitions.…”

Section: Resultsmentioning

confidence: 99%

Self-Assembled Tetra- and Pentanuclear Nickel(II) Aggregates From Phenoxido-Based Ligand -Bound {Ni₂} Fragments: Carboxylate Bridge Controlled Structures

et al. 2013

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Three different carboxylato bridges (R = C2H5, CF3, and PhCH2 in RCO2(-)) have been used to obtain the supramolecular aggregates [Ni5(μ-H2bpmp)2(μ3-OH)2(μ1,3-O2CC2H5)6]·2H2O·4DMF (1·2H2O·4DMF), [Ni4(μ3-H2bpmp)2(μ3-OH)2(μ1,3-O2CCF3)2](CF3CO2)2·H2O (2·H2O), and [Ni4(μ3-H2bpmp)2(μ3-OH)2(μ1,3-O2CCH2Ph)2](PhCH2CO2)2·4H2O (3·4H2O) (H3bpmp =2,6-bis-[(3-hydroxy-propylimino)-methyl]-4-methyl-phenol) from the hydroxido-bridged dinuclear motif [Ni2(μ-H2bpmp)(OH)](2+). These complexes have been characterized by X-ray crystallography and magnetic measurements. A change from propanoate group to trifluoroacetate and phenylaceate groups provided different course of cluster assembly based on Ni2(μ-H2bpmp)2 fragments. The {Ni5(μ3-OH)2(μ1,3-O2CC2H5)6}(2+) core in 1 contains five Ni(II) ions in an hourglass (pentanuclear vertex-shared double cubane) arrangement. These compounds are new examples of [Ni5] and [Ni4] complexes where aggregation of the building motifs are guided by the nature of the carboxylate anions, which allows an effective tuning of the self-aggregate process within same ligand environment. The study of the magnetic properties reveals that 1 exhibits an S = 3 ground state. Nevertheless, the magnetization increases above the expected saturation value of 6 μB at higher fields, because of the suppression of antiferromagnetic exchange between the central and peripheral Ni(II) ions. Complexes 2 and 3 exhibit ferromagnetic exchange interactions that result in the S = 4 ground state. Examination of AC magnetic susceptibility showed that complex 2 in finely ground form behaves as spin glass with the spin-freezing temperature of ∼5.5 K. This behavior was attributed to the collapse of the structure upon the loss of interstitial solvent. Such property was not observed for complex 3, in which the bulkier carboxylate ligands provide for a more robust crystal packing and larger separation between the [Ni4O4] clusters.

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New Mixed‐Metal Aggregates Derived From Dinickel Complexes on a 2‐Formylphenolate Template: Counteranion Dependent Formation of 1D Chain and Discrete NaNi₂ Complexes

Abstract: Diagnostic considerations

Cited by 15 publications

References 48 publications

A New Family of Ni₄ and Ni₆ Aggregates from the Self-Assembly of [Ni₂] Building Units: Role of Carboxylate and Carbonate Bridges

A New Family of Ni₄ and Ni₆ Aggregates from the Self-Assembly of [Ni₂] Building Units: Role of Carboxylate and Carbonate Bridges

(Ni₂), (Ni₃), and (Ni₂+ Ni₃): A Unique Example of Isolated and Cocrystallized Ni₂and Ni₃Complexes

Self-Assembled Tetra- and Pentanuclear Nickel(II) Aggregates From Phenoxido-Based Ligand -Bound {Ni₂} Fragments: Carboxylate Bridge Controlled Structures

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New Mixed‐Metal Aggregates Derived From Dinickel Complexes on a 2‐Formylphenolate Template: Counteranion Dependent Formation of 1D Chain and Discrete NaNi2 Complexes

Abstract: Diagnostic considerations

Cited by 15 publications

References 48 publications

A New Family of Ni4 and Ni6 Aggregates from the Self-Assembly of [Ni2] Building Units: Role of Carboxylate and Carbonate Bridges

A New Family of Ni4 and Ni6 Aggregates from the Self-Assembly of [Ni2] Building Units: Role of Carboxylate and Carbonate Bridges

(Ni2), (Ni3), and (Ni2+ Ni3): A Unique Example of Isolated and Cocrystallized Ni2and Ni3Complexes

Self-Assembled Tetra- and Pentanuclear Nickel(II) Aggregates From Phenoxido-Based Ligand -Bound {Ni2} Fragments: Carboxylate Bridge Controlled Structures

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New Mixed‐Metal Aggregates Derived From Dinickel Complexes on a 2‐Formylphenolate Template: Counteranion Dependent Formation of 1D Chain and Discrete NaNi₂ Complexes

A New Family of Ni₄ and Ni₆ Aggregates from the Self-Assembly of [Ni₂] Building Units: Role of Carboxylate and Carbonate Bridges

A New Family of Ni₄ and Ni₆ Aggregates from the Self-Assembly of [Ni₂] Building Units: Role of Carboxylate and Carbonate Bridges

(Ni₂), (Ni₃), and (Ni₂+ Ni₃): A Unique Example of Isolated and Cocrystallized Ni₂and Ni₃Complexes

Self-Assembled Tetra- and Pentanuclear Nickel(II) Aggregates From Phenoxido-Based Ligand -Bound {Ni₂} Fragments: Carboxylate Bridge Controlled Structures