Multidimensional Metal−Organic Frameworks Constructed from Flexible Bis(imidazole) Ligands

Cui, Guang‐Hua; Lǐ, Jiànróng; Tian, Jin‐Lei; Bu, Xian‐He; Batten, Stuart Robert

doi:10.1021/cg050039l

Cited by 217 publications

(55 citation statements)

References 48 publications

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“…The most impressive examples of this last category are zeolitic imidazolate frameworks (ZIFs). [48][49][50][51][52] The ZIFs, a subclass of MOFs, have frameworks that closely resembles that of zeolites, with a metal-imidazolate-metal angle of 1458 replacing the zeolites' SiÀOÀSi angle of the same value. The strong constraint on the porous framework imposed by the fixed value of this angle severely limits the flexibility of the ZIFs, as is the case for zeolites, implying a similar lattice energy/density trend than in zeolites.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Methods and Models to Study Flexible Metal–Organic Frameworks

et al. 2011

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Much attention has recently been focused on a fascinating subclass of metal-organic frameworks that behave in a remarkable stimuli-responsive fashion. These soft porous crystals feature dynamic crystalline frameworks displaying reversible, large-amplitude structural deformations under external physical constraints such as temperature, electric field or gas exposure. The number of reported syntheses of such materials is rapidly growing and they are promising for practical applications, such as gas capture, purification and fluid separation. Herein, we summarize the recently developed thermodynamic tools that can help understand the process of fluid adsorption and fluid mixture coadsorption in these flexible nanoporous materials. These tools, which include both molecular simulation methods and analytical models, can help rationalize experimental results and predict adsorption properties over a wide range of thermodynamic conditions. A particular focus is given on how these methods can guide the experimental exploration of a large number of materials and working conditions (temperature, pressure, composition) to help design efficient processes relying on fluid adsorption in soft porous crystals.

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Section: Introductionmentioning

confidence: 99%

Thermodynamic Methods and Models to Study Flexible Metal–Organic Frameworks

et al. 2011

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“…[25,37,38] Based upon these observations, a general view has formed that ion exchange processes in coordination polymers take place through a solidstate diffusion mechanism. [25,[29][30][31][32][33][34][35][36]39] Such a solid-state mechanism implies that ion exchange proceeds through the diffusion of free ions within channels of coordination polymer crystals or microcrystals. [40,41] Recently, we have demonstrated [42,43] that ion exchange in Ag I polymers with heterocyclic ligands occurs through a solvent-mediated mechanism [44] and not through a solid-state process.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Equilibria in Solvent‐Mediated Anion, Cation and Ligand Exchange in Transition‐Metal Coordination Polymers: Solid‐State Transfer or Recrystallisation?

Cui

Khlobystov

Chen

et al. 2009

Chemistry A European J

117

119

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The solution properties of a series of transition-metal-ligand coordination polymers [ML(X)(n)](infinity) [M=Ag(I), Zn(II), Hg(II) and Cd(II); L=4,4'-bipyridine (4,4'-bipy), pyrazine (pyz), 3,4'-bipyridine (3,4'-bipy), 4-(10-(pyridin-4-yl)anthracen-9-yl)pyridine (anbp); X=NO(3) (-), CH(3)COO(-), CF(3)SO(3) (-), Cl(-), BF(4) (-); n=1 or 2] in the presence of competing anions, metal cations and ligands have been investigated systematically. Providing that the solubility of the starting complex is sufficiently high, all the components of the coordination polymer, namely the anion, the cation and the ligand, can be exchanged on contact with a solution phase of a competing component. The solubility of coordination polymers is a key factor in the analysis of their reactivity and this solubility depends strongly on the physical properties of the solvent and on its ability to bind metal cations constituting the backbone of the coordination polymer. The degree of reversibility of these solvent-induced anion-exchange transformations is determined by the ratio of the solubility product constants for the starting and resultant complexes, which in turn depend upon the choice of solvent and the temperature. The extent of anion exchange is controlled effectively by the ratio of the concentrations of incoming ions to outgoing ions in the liquid phase and the solvation of various constituent components comprising the coordination polymer. These observations can be rationalised in terms of a dynamic equilibrium of ion exchange reactions coupled with Ostwald ripening of crystalline products. The single-crystal X-ray structures of [Ag(pyz)ClO(4)](infinity) (1), {[Ag(4,4'-bipy)(CF(3)SO(3))]CH(3)CN}(infinity) (2), {[Ag(4,4'-bipy)(CH(3)CN)]ClO(4) 0.5 CH(3)CN}(infinity) (3), metal-free anbp (4), [Ag(anbp)NO(3)(H(2)O)](infinity) (5), {[Cd(4,4'-bipy)(2)(H(2)O)(2)](NO(3))(2)4 H(2)O}(infinity) (6) and {[Zn(4,4'-bipy)SO(4)(H(2)O)(3)] 2 H(2)O}(infinity) (7) are reported.

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“…The ligands L 1 -L 3 were prepared according to literature methods [32]. Elemental analyses were obtained on a Perkin-Elmer automatic analyzer.…”

Section: Materials and General Methodsmentioning

confidence: 99%

Assembly of Three Cadmium(II) Complexes Based on Flexible α,ѡ-Bis(benzimidazolyl)alkane Ligands

Geng

Jiao

Cui

2012

Zeitschrift Für Naturforschung B

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Three flexible α, ω-bis(5,6-dimethylbenzimidazolyl)alkane ligands with different spacers were reacted with CdX 2 (X = Cl, Br, I) hydrothermally, resulting in three coordination archi-. They have been characterized by elemental analyses, IR spectra, thermogravimetric (TG) analysis, and single-crystal X-ray diffraction. Complex 1 displays a helical chain linked by the ligands L 1 , and a 2D supramolecular network is constructed through π−π stacking interactions; complex 2 shows a helical chain structure with connections through two kinds of strong π−π stacking interactions into an intricate 3D supramolecular network; complex 3 contains dinuclear metallomacrocycles. The fluorescence properties of 1-3 have been investigated in the solid state.

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Multidimensional Metal−Organic Frameworks Constructed from Flexible Bis(imidazole) Ligands

Cited by 217 publications

References 48 publications

Thermodynamic Methods and Models to Study Flexible Metal–Organic Frameworks

Thermodynamic Methods and Models to Study Flexible Metal–Organic Frameworks

Dynamic Equilibria in Solvent‐Mediated Anion, Cation and Ligand Exchange in Transition‐Metal Coordination Polymers: Solid‐State Transfer or Recrystallisation?

Assembly of Three Cadmium(II) Complexes Based on Flexible α,ѡ-Bis(benzimidazolyl)alkane Ligands

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