Syntheses, magnetic properties, and crystal structures of the dimers [LNi(µ-N3)3NiL](ClO4) and [L′2Ni2(N3)2(µ-N3)2](L =N,N′,N″-trimethyl-1,4,7-triazacyclononane; L′= 1,5,9-triazacyclododecane); µ-triazido-vs. µ-diazido-bridging

Chaudhuri, Phalguni; Guttmann, M.; Ventur, D.; Wieghardt, Karl; Nuber, Bernhard; Weiß, Johannes

doi:10.1039/c39850001618

Cited by 63 publications

(15 citation statements)

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“…In general, the end‐to‐end coordination mode results in antiferromagnetically coupled compounds,1,8–13 whereas the end‐on coordination gives ferromagnetically coupled compounds 1,14,16,17. However, deviation may exist in certain cases for example in the single end‐to‐end bridged azido 1D compound [Ni(5‐methylpyrazole) 4 (μ 1,3 ‐N 3 )] n (ClO 4 ) n ferromagnetic coupling with an exchange coupling constant J = 6.5 cm –1 was reported 15.…”

Section: Introductionmentioning

confidence: 99%

Dinuclear and Polynuclear Bridged Azido–Nickel(II) Complexes: Synthesis, Structure Determination, and Magnetic Properties

et al. 2007

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Me 6 trien = 1,1,4,7,10,10-hexamethyltriethylene tetramine} were synthesized and structurally characterized by spectroscopic techniques, X-ray crystallography, and variable-temperature magnetic measurements. In the complexes 1-3a, the ClO 4 -groups are counterions and the Ni 2+ centers are bridged by the azido ligands in an end-to-end bonding fashion. The coordination geometry around the Ni II ions is six-coordinate with a distorted octahedral environment achieved by the four N atoms of the tetradentate amines and two terminal N atoms of the azide groups. Complex 1 consists of dinuclear units with doubly bridged azido groups whereas in 2 and 3a, a polymeric 1D chain is formed in which the adjacent azido

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Section: Introductionmentioning

confidence: 99%

Dinuclear and Polynuclear Bridged Azido–Nickel(II) Complexes: Synthesis, Structure Determination, and Magnetic Properties

et al. 2007

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“…The versatility of this ligand is due to its diverse binding modes leading to a variation in the magnetic properties that depend on its orientation with respect to the magnetic centers 18. In general, the bridging modes observed for the azido group are end‐to‐end with anti‐ferromagnetic interaction19,20 and end‐on with ferromagnetic interaction 21. However, the magnetism of the latter is dependent on the M−N−M angle 22−27.…”

Section: Introductionmentioning

confidence: 99%

Three Novel End-to-End Single Azido-Bridged Ferromagnetic Copper(II) Chains: Synthesis, Crystal Structure, and Magnetic Behavior

Mukherjee

Maji

Escuer

et al. 2002

Eur. J. Inorg. Chem.

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Three new single end‐to‐end azido‐bridged copper(II) chains [Cu(L1)(N3)]n(ClO4)n (1), [Cu(L2)(N3)]n(ClO4)n (2), and [Cu(L3)(N3)]n(ClO4)n (3) using three different tridentate Schiff bases L1, L2, and L3, obtained from condensation of pyridine‐2‐carbaldehyde with N,N‐dimethylethane‐1,2‐diamine, N,N‐diethylethane‐1,2‐diamine, and 4‐(2‐aminoethyl)morpholine, respectively, have been synthesized, and their crystal structures have been determined by X‐ray diffraction methods. Complex 1, C10H15CuN6ClO4, crystallizes in an orthorhombic system, space group P212121, with a = 7.434(3), b = 12.047(4), c = 17.404(6) Å, and Z = 4; complex 2, C12H19CuN6ClO4, crystallizes in an orthorhombic system, space group Pna21, with a = 14.723(5), b = 13.829(5), c = 8.002(5) Å, and Z = 4 and complex 3, C12H17CuN6ClO5, crystallizes in an orthorhombic system, space group Pna21, with a = 13.837(15), b = 14.804(2), c = 8.050(4) Å, and Z = 4. Each structure consists of a single end‐to‐end azido‐bridged copper(II) 1D chain where each copper(II) center possesses a square pyramidal geometry. Magnetic susceptibility data, measured from 4 to 300 K, show weak ferromagnetic interaction through the end‐to‐end bridging azido pathway in all the complexes. The magnetic data were fitted to a high temperature series‐expansion for a one‐dimensional system with S = 1/2 local spin based on the Hamiltonian H = −JΣSi·Si+1 for all the complexes, giving the parameters J = +2.15 cm−1, g = 2.23 for 1, J = +3.61 cm−1, g = 2.16 for 2, and J = +2.06 cm−1, g = 2.17 for 3. This unusual magnetic behavior through the end‐to‐end bridging azido pathway has been correlated to the structural parameters. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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“…At 298. 15(2) K, the complexation free energy rG for N3  binding, was found to be 27.8(2) kJ mol -1 , corresponding to an association constant of log K11 = 4.88(4) (Table 3). Analysis of the ITC data sets recorded for binding of F  and Cl  to 3 revealed that the F  ion is bound more strongly than N3  (rG = -39.0(4) kJ mol -1 , log K11 = 6.84( 7)), while the Cl  is bound less strongly than N3  (rG = -20.1(3) kJ mol -1 , log K11 = 3.52( 5)).…”

Section: Determination Of Stability Constantsmentioning

confidence: 99%

“…13 Beer et al, for example, have appended two triazacyclononane rings (tacn) on a calixarene backbone and the three bridging azido ligands in the corresponding Ni2 complex all act as end-on bridges. 14 This compound should be compared with the unmodified [(Me3tacn)2Ni2(N3)3] + system, which appears in three forms, one with three end-on bridges as in Beer's compound, 10 one form with three end-to-end bridges, 15 and the third one with only two end-to-end bridges. In another relevant study, Escuer et al used a dinuclear cryptate of ellipsoidal shape to enforce the end-to-end mode in a Ni II complex.…”

Section: Introductionmentioning

confidence: 99%

Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni^II₂(L)(μ_1,1-N₃)][ClO₄] (L = Macrocyclic N₆S₂ Ligand)

et al. 2016

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The dinuclear Ni(II) complex [Ni2(L(2))][ClO4]2 (3) supported by the 28-membered hexaaza-dithiophenolate macrocycle (L(2))(2-) binds the N3(-) ion specifically end-on yielding [Ni2(L(2))(μ(1,1)-N3)][ClO4] (7) or [Ni2(L(2))(μ(1,1)-N3)][BPh4] (8), while the previously reported complex [Ni2L(1)(μ(1,3)-N3)][ClO4] (2) of the 24-membered macrocycle (L(1))(2-) coordinates it in the end-to-end fashion. A comparison of the X-ray structures of 2, 3, and 7 reveals the form-selective binding of complex 3 to be a consequence of its preorganized, channel-like binding pocket, which accommodates the azide anion via repulsive CH···π interactions in the end-on mode. In contrast to [Ni2L(1)(μ(1,3)-N3)][ClO4] (2), which features a S = 0 ground state, [Ni2(L(2))(μ(1,1)-N3)][BPh4] (8) has a S = 2 ground state that is attained by competing antiferromagnetic and ferromagnetic exchange interactions via the thiolato and azido bridges with a value for the magnetic exchange coupling constant J of 13 cm(-1) (H = -2JS1S2). These results are further substantiated by density functional theory calculations. The stability of the azido-bridged complex determined by isothermal titration calorimetry in MeCN/MeOH 1/1 v/v (log K11 = 4.88(4) at I = 0.1 M) lies in between those of the fluorido- (log K11 = 6.84(7)) and chlorido-bridged complexes (log K11 = 3.52(5)). These values were found to compare favorably well with the equilibrium constants derived at lower ionic strength (I = 0.01 M) by absorption spectrophotometry (log K11 = 5.20(1), 7.77(9), and 4.13(3) for N3(-), F(-), and Cl(-) respectively).

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Syntheses, magnetic properties, and crystal structures of the dimers [LNi(µ-N₃)₃NiL](ClO₄) and [L′₂Ni₂(N₃)₂(µ-N₃)₂](L =N,N′,N″-trimethyl-1,4,7-triazacyclononane; L′= 1,5,9-triazacyclododecane); µ-triazido-vs. µ-diazido-bridging

Cited by 63 publications

References 0 publications

Dinuclear and Polynuclear Bridged Azido–Nickel(II) Complexes: Synthesis, Structure Determination, and Magnetic Properties

Dinuclear and Polynuclear Bridged Azido–Nickel(II) Complexes: Synthesis, Structure Determination, and Magnetic Properties

Three Novel End-to-End Single Azido-Bridged Ferromagnetic Copper(II) Chains: Synthesis, Crystal Structure, and Magnetic Behavior

Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni^II₂(L)(μ_1,1-N₃)][ClO₄] (L = Macrocyclic N₆S₂ Ligand)

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Syntheses, magnetic properties, and crystal structures of the dimers [LNi(µ-N3)3NiL](ClO4) and [L′2Ni2(N3)2(µ-N3)2](L =N,N′,N″-trimethyl-1,4,7-triazacyclononane; L′= 1,5,9-triazacyclododecane); µ-triazido-vs. µ-diazido-bridging

Cited by 63 publications

References 0 publications

Dinuclear and Polynuclear Bridged Azido–Nickel(II) Complexes: Synthesis, Structure Determination, and Magnetic Properties

Dinuclear and Polynuclear Bridged Azido–Nickel(II) Complexes: Synthesis, Structure Determination, and Magnetic Properties

Three Novel End-to-End Single Azido-Bridged Ferromagnetic Copper(II) Chains: Synthesis, Crystal Structure, and Magnetic Behavior

Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [NiII2(L)(μ1,1-N3)][ClO4] (L = Macrocyclic N6S2 Ligand)

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Syntheses, magnetic properties, and crystal structures of the dimers [LNi(µ-N₃)₃NiL](ClO₄) and [L′₂Ni₂(N₃)₂(µ-N₃)₂](L =N,N′,N″-trimethyl-1,4,7-triazacyclononane; L′= 1,5,9-triazacyclododecane); µ-triazido-vs. µ-diazido-bridging

Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni^II₂(L)(μ_1,1-N₃)][ClO₄] (L = Macrocyclic N₆S₂ Ligand)