Determination of the Solvothermal Synthesis Mechanism of Metal Imidazolates by X‐ray Single‐Crystal Studies of a Photoluminescent Cadmium(<scp>II</scp>) Imidazolate and Its Intermediate Involving Piperazine

Tian, Yuan; Xu, Li; Cai, Chenxin; Wei, Jichong; Li, Yi‐Zhi; You, Xiao‐Zeng

doi:10.1002/ejic.200300560

Cited by 31 publications

(10 citation statements)

References 15 publications

(11 reference statements)

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“…5) the conversion takes place rather sharply and involves the dissolution of a significant fraction (#0.5) of the intermediate neb phase before coi starts crystallising, suggesting that the conversion is not a solid-solid transformation but rather a solution-mediated recrystallisation process as might be expected from the different framework topologies and chemical compositions. While crystalline intermediates during ZIF formation have been reported previously, 9,23 this is the first direct in situ monitoring of a ZIF conversion process in solution. We speculate that nucleation of the coi phase takes place heterogeneously on the surfaces of still available neb particles.…”

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confidence: 61%

Subtle polymorphism of zinc imidazolate frameworks: temperature-dependent ground states in the energy landscape revealed by experiment and theory

et al. 2013

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We show by variable-temperature X-ray diffraction and differential scanning calorimetry experiments that zinc imidazolates with coi and zni framework topology, respectively represent the thermodynamically stable phase below and above a transition temperature of #360 uC at ambient pressure. The relative stability of the two polymorphs and the experimentally observed strong negative thermal expansion of the coi phase at high temperatures close to the phase transition were successfully modelled using density functional theory calculations. A novel metastable zinc imidazolate with neb framework topology was detected by in situ X-ray diffraction experiments as a transient crystalline phase during solvothermal crystallisation of the stable coi phase.Zeolitic imidazolate frameworks (ZIFs) represent a new class of technology relevant microporous materials that are at the focus of current research efforts. 1,2 Important characteristics of ZIFs are comparatively high thermal and chemical stabilities and the ability to crystallise in a large variety of topologically different frameworks which may be tailored for a specific application in gas storage, separation, sensing or catalysis. ZIFs consist of tetrahedral cationic centres (Zn II , Co II , Fe II , Cd II , and also Li I /B III ) connected by imidazolate-based bridging ligands. Because of the local tetrahedral geometry of metal connectors and the metal-imidazolatemetal bridging angle of #145u ZIFs adopt network topologies common for microporous silica polymorphs and zeolites. Recent studies have revealed that ZIFs may undergo thermally-and/or pressure-induced amorphisation that reinforces the similarity between ZIFs and silica. [3][4][5] However, important differences between ZIFs and silica systems are still ignored in the literature. For example, it is well known that the thermodynamic 'ground state' of the silica system at ambient conditions corresponds to the a-quartz phase (qtz net) 6 , whereas the quartz-like topology is hardly accessible in the Zn(im) 2 (im = imidazolate) system as was shown in our previous ab initio study. 7,8 By considering only unsubstituted imidazolate bridging ligands, nine topologically different Zn(im) 2 frameworks have been experimentally realised to date (zni, coi, cag, mer, gis, dft, crb, zec, nog) 1,2,9 and even more are predicted to be synthetically accessible. 7 However, up to now there was no experimental study which addressed the important question about the thermodynamically most stable phase(s) ('ground state(s)') in the Zn(im) 2 system, which might be either of the two most dense phases zni or coi. Recently, an irreversible single-crystal-to-single-crystal pressureinduced phase transition from the zni to the coi phase was observed at room temperature by Spencer et al. 10 revealing that coi is stable at high pressures (>0.55 GPa). The polymorphs with zni and coi underlying nets crystallise in the tetragonal space groups I4 1 cd and I4 1 , respectively, and are closely related to each other since both frameworks may be considered ...

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confidence: 61%

Subtle polymorphism of zinc imidazolate frameworks: temperature-dependent ground states in the energy landscape revealed by experiment and theory

et al. 2013

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“…Fluorescence emission intensity of the imidazole ligand is generally weak. The ligand's contribution to the fluorescence properties of the complex is very limited . The greatly improved emission intensity in the perovskite compound 1 can be attributed to two factors.…”

Section: Resultsmentioning

confidence: 99%

Novel 〈110〉-Oriented Organic−Inorganic Perovskite Compound Stabilized by N-(3-Aminopropyl)imidazole with Improved Optical Properties

et al. 2006

Chem. Mater.

143

130

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In the organic−inorganic perovskites family, the 〈100〉-oriented type has been extensively investigated as a result of its unique magnetic, optical, and electrical properties, and only one type of 〈110〉-oriented hybrid perovskite stabilized by methylammonium and iodoformamidinium cations or the latter themselves has been known so far. In this paper, another novel 〈110〉-oriented organic−inorganic perovskite (C6H13N3)PbBr4 (compound 1) has been prepared by reacting N-(3-aminopropyl)imidazole (API) with PbBr2 in hydrobromic acid. The crystal structure is determined, which indicates that the perovskite is stabilized by API. The introduction of the optically active organic ligand API into the hybrid perovskite results in a red shift and a great enhancement of photoluminescence in the perovskite with respect to organic ligand API itself. These results have been explained according to calculation based on density-functional theory. Moreover, the excellent film processing ability for the perovskite (C6H13N3)PbBr4 together with the improved optical properties makes it have potential application in optoelectronic devices.

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“…By employing cobalt(II) imidazolate polymer as an organic silica analogue, we have obtained a porous zeolite-like structure 7a and some silica-like extended frameworks with structural features of zeolites. 7b More interesting is that the cobalt(II) imidazolate synthesis is also reminiscent of the zeolite synthetic feature although its reaction mechanism 11 is quite different from that of the zeolite synthesis; 12 however, the same topological structures of cobalt(II) imidazolate can be generated by using different templates 7b just similar to the zeolite synthesis. Can different structures of cobalt(II) imidazolate also be generated by using the same template as in the zeolitic synthesis that will imply the existence of further extended polymorphism of the substance?…”

Section: Introductionmentioning

confidence: 99%

Two Polymorphs of Cobalt(II) Imidazolate Polymers Synthesized Solvothermally by Using One Organic Template N,N-Dimethylacetamide

et al. 2004

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Two structurally different polymorphs of cobalt(II) imidazolate frameworks are solvothermally synthesized by using N,N-dimethylacetamide as a template: The polymorph 6 (a = 9.797 (4) angstroms, b = 15.301(6) angstroms, c =14.902(6) angstroms, beta = 98.904(6) degrees, monoclinic, P21/n) shows structures of silicate CaAl2Si2O8 with CrB4 topology, while polymorph 7 (a = 15.173(4) angstroms, b = 15.173(4) angstroms, c = 19.089(5) angstroms, Pbca) shows CaGa2O4-related topological structures. In addition, the 7' (a = 15.9712(18) angstroms, b = 15.9253(19) angstroms, c = 18.475(2) angstroms, Pbca), a compound isostructural with 7, is synthesized by using cyclohexanol as a template. Thus, these cobalt(II) imidazolate polymers are reminiscent of the zeolite syntheses in that not only the same topological structure can be synthesized by using the different organic templates, but also different topological structures can be synthesized by using the same organic template.

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Determination of the Solvothermal Synthesis Mechanism of Metal Imidazolates by X‐ray Single‐Crystal Studies of a Photoluminescent Cadmium(II) Imidazolate and Its Intermediate Involving Piperazine

Cited by 31 publications

References 15 publications

Subtle polymorphism of zinc imidazolate frameworks: temperature-dependent ground states in the energy landscape revealed by experiment and theory

Subtle polymorphism of zinc imidazolate frameworks: temperature-dependent ground states in the energy landscape revealed by experiment and theory

Novel 〈110〉-Oriented Organic−Inorganic Perovskite Compound Stabilized by N-(3-Aminopropyl)imidazole with Improved Optical Properties

Two Polymorphs of Cobalt(II) Imidazolate Polymers Synthesized Solvothermally by Using One Organic Template N,N-Dimethylacetamide

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