Synthesis, crystal structure and luminescent properties of transition metals complexes based on imidazole derivatives

Yue, Shijing; Li, Na; Bian, Jiangyu; Hou, Tingting; Ma, Jian‐Fang

doi:10.1016/j.synthmet.2011.11.030

Cited by 17 publications

(9 citation statements)

References 29 publications

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“…An alternative route to design cyanido-bridged d–f oligonuclear species or chains is the use of an auxiliary ligand that can block several coordination sites of the lanthanide(III) ions. − For example, in the case of cyanido-bridged {Ln III M V } complexes, the tridentate 2,2′:6′,2″-terpyridine (terpy) ligand favored the formation of binuclear and chain structures, , while the bis-bidentate 2,2′-bipyrimidine (bpym) molecule in its reaction with cerium(III) and {W V (CN) 8 } 3– ions afforded tetranuclear complexes, where the polyazine ligand bridges the rare-earth cations . By using pyridine bis(oxazoline)-type molecules as capping ligands, magneto-chiral and/or luminescent cyanido-bridged {Ln III W V } chains were obtained. ,, From the rich library of chelating pyridine-based agents, the 2-(1 H -imidazol-2-yl)-pyridine (pyim) molecule proved to be a versatile ligand toward transition metal ions, being able to adopt bidentate − and bridging bis-monodentate (under imidazole deprotonation) coordination modes or having a functional role in the iron(II) spin-crossover complexes. − To our knowledge, there is no example of pyim-containing lanthanide(III) complexes.…”

Section: Introductionmentioning

confidence: 99%

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

et al. 2017

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A new series of cyanido-bridged {LnW} heterobinuclear complexes of formula [Ln(pyim)(i-PrOH)(HO)(μ-CN)W(CN)]·2HO [Ln = Gd (1), Tb (2), Dy (3), Ho (4), and Er (5); pyim = 2-(1H-imidazol-2-yl)-pyridine) and i-PrOH = isopropyl alcohol] were synthesized by one-pot reaction between (NHBu)[W(CN)] and [Ln(pyim)] complexes (generated in situ by mixing the corresponding Ln ions and the pyim ligand). Compounds 1-5 are isomorphous and crystallize in the monoclinic system P2/n space group. Their crystal structure consists of binuclear units in which the octacyanotungstate(V) anion coordinates to the corresponding Ln ion through a single cyanide ligand. The tungsten(V) and lanthanide(III) ions are eight-coordinated, in distorted square antiprism (W) and distorted trigonal dodecahedron (Ln) geometries, respectively. The direct-current (dc) magnetic properties for 1-5 reveal the occurrence of weak antiferromagnetic interactions between W and Ln cation, with S, F, H, I, and I as ground terms for Gd, Tb, Dy Ho, and Er, respectively [J = -1.19(1) (1), -1.02(2) (2), -1.10(2) (3), -1.30(2) (4), and -1.50(3) cm (5), the spin Hamiltonian being defined as H = -J S·S]. The fit of the χT data of 2-4 points out a positive value for the energy gap between the M components (Δ). This feature is corroborated by their Q-band electron paramagnetic resonance spectra at low temperature, which clearly show M = 0 (2 and 4) and ±1/2 (3 and 5). Incipient frequency-dependent alternating-current magnetic susceptibility signals are observed for 3 and 5 under applied dc fields supporting the presence of slow magnetic relaxation behavior, the blocking temperatures being below 2.0 K. This new series of {LnW} heterobinuclear compounds provides more insights into the exchange magnetic interaction between 5d and 4f centers via the cyanide-bridge, for which scarce information is available to date.

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Section: Introductionmentioning

confidence: 99%

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

et al. 2017

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“…Switching solvents to DMF (a hydrogen bond acceptor only), the previously reported Mn(BBP)Cl 2 • DMF is a convenient starting point for this analysis. 36,37 In this case, the DMF does not participate through metal coordination, but rather it acts as a hydrogen bonding acceptor to one of the NH imidazole groups (Figure 4a). By acting in a capping fashion, this building motif prevents the formation of an extended hydrogen bonding network.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

The Role of Hydrogen Bonds in Facilitating Planar Alignment of Mn(II) Halide 2,6-Bis(benzimidazole)pyridine-Based Complexes

Thompson

Williams

Leznoff

2017

Crystal Growth & Design

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A series of Mn(II) halide complexes has been synthesized with 2,6-bis(benzimidazole)-pyridine (BBP), 2,6-bis(N-methyl-benzimidazole)pyridine (MBBP), and 2,6-bis(benzathiazole)-pyridine (BBTP) ligands in solvents capable of acting as hydrogen bonding donors and/or acceptors, resulting in Mn(BBP)(EtOH)X2 (X = Cl, Br), Mn(BBP)Br2·DMF, Mn(BBP)Br2·MeCN, Mn(MBBP)X2 (X = Cl, Br), [Mn(MBBP)(Br)(MeOH)2][Br] and Mn(BBTP)X2 (X = Cl, Br). The crystal structures of these materials were analyzed for the degree of planar packing of the anisotropic ligands. The exchange of hydrogen bonding donor and acceptor solvents (ethanol) for solvents only capable of accepting hydrogen bonds (DMF, acetonitrile) decreased the role of the solvent in the hydrogen bonding networks and also capped the NH groups of BBP, reducing the effectiveness of the BBP to form extended networks. Replacing NH groups in BBP with N-methyl groups (MBBP) and sulfur (BBTP) reduced the number of strong interactions between complexes, leading to a greater tendency for nonplanar crystal packing of the ligands. The effect of poorly oriented anisotropic ligands within the structures results in lower birefringence (Δn) values of 0.229(10) and 0.23(3) for Mn(BBP)Cl2·DMF and Mn(MBBP)Br2, respectively. Compounds Mn(BBP)(EtOH)X2 (X = Cl, Br) were found to have good stacking of BBP units, leading to a highly anisotropic structure and a Δn value of 0.538(3) for Mn(BBP)(EtOH)Br2.

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“…Contrastively, the free pyim ligand displays very weak emission at 370 nm in the UV region. 33 The maximum emission of 1 has a red shift, which probably is assigned to π-π* transition fluorescence. The enhanced fluorescence efficiency of 1 is attributed to the coordination of the pyim ligand to the Zn 2+ ions that effectively increases the rigidity of pyim ligand and reduces the loss of energy by thermal vibrations.…”

Section: Fluorescence Spectrummentioning

confidence: 99%

Syntheses, structures and properties of two 2-D layered hybrid organic–inorganic materials based on different V₄O₁₂building units

Hou

Guo

et al. 2014

Dalton Trans.

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Two new layered hybrid organic-inorganic compounds [Zn(pyim)]2V4O12 () (pyim = 2-(2-pyridyl)imidazole) and [Cu(bim)2]2V4O12(H2O)·CH3CH2OH () (bim = bis(1-imidazolyl)methane) based on polyoxovanadates (POVs) and organic ligands decorated transition metal units have been synthesized by hydrothermal and solvothermal methods respectively. Single crystal XRD, fluorescence spectrum, magnetic measurement, IR spectra, powder XRD and thermogravimetric (TG) measurements were performed to analyze the structures and properties of and . The structural analysis reveals that compound features a two-dimensional {[Zn(pyim)]2V4O12}n layered structure, constructed by sine wave-like {V4O12}n(4n-) chains, Zn(2+) ions and pyim ligands. In the layered structure of , {V4O12}(4-) circles are connected by Cu(2+) ions to form {Cu(V4O12)}n(2n-) chains, which are further linked by {Cu(bim)4}(2+) subunits to generate a hybrid layer of . The magnetic susceptibility measurement indicates strong antiferromagnetic interactions between Cu(2+) ions in .

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Synthesis, crystal structure and luminescent properties of transition metals complexes based on imidazole derivatives

Cited by 17 publications

References 29 publications

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

The Role of Hydrogen Bonds in Facilitating Planar Alignment of Mn(II) Halide 2,6-Bis(benzimidazole)pyridine-Based Complexes

Syntheses, structures and properties of two 2-D layered hybrid organic–inorganic materials based on different V₄O₁₂building units

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Synthesis, crystal structure and luminescent properties of transition metals complexes based on imidazole derivatives

Cited by 17 publications

References 29 publications

Cyanido-Bridged {LnIIIWV} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Cyanido-Bridged {LnIIIWV} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

The Role of Hydrogen Bonds in Facilitating Planar Alignment of Mn(II) Halide 2,6-Bis(benzimidazole)pyridine-Based Complexes

Syntheses, structures and properties of two 2-D layered hybrid organic–inorganic materials based on different V4O12building units

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Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Syntheses, structures and properties of two 2-D layered hybrid organic–inorganic materials based on different V₄O₁₂building units