Self-assembly of three new metal organic coordination networks based on 1,2-bis(imidazol-1yl-methyl)benzene

Polyhedron ◽  
2015 ◽  
Vol 102 ◽  
pp. 1-7 ◽  
Author(s):  
Fatih Semerci ◽  
Okan Zafer Yeşilel ◽  
Fatma Yüksel
2014 ◽  
Vol 50 (97) ◽  
pp. 15327-15329 ◽  
Author(s):  
Tao Lin ◽  
Guowen Kuang ◽  
Xue Song Shang ◽  
Pei Nian Liu ◽  
Nian Lin

A two-step strategy consisting of on-surface synthesis and supramolecular assembly is developed for constructing low-dimensional molecular nanostructures on surfaces.


2016 ◽  
Vol 72 (11) ◽  
pp. 895-900
Author(s):  
Xin-Hua Lu ◽  
Kai-Long Zhong

The self-assembly of coordination polymers and the crystal engineering of metal–organic coordination frameworks have attracted great interest, but it is still a challenge to predict and control the compositions and structures of the complexes. Employing multidentate organic ligands and suitable metal ions to construct inorganic–organic hybrid materials through metal–ligand coordination and hydrogen-bonding interactions has become a major strategy. Recently, imidazole-containing multidentate ligands that contain an aromatic core have received much attention. A new three-dimensional MnIIcoordination polymer based on 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene, namely poly[(ethane-1,2-diol-κO)(μ-sulfato-κ2O:O′){μ3-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ3N:N′:N′′}manganese(II)], [Mn(SO4)(C18H18N6)(C2H6O2)]n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that there are two kinds of crystallographically independent MnIIcentres, each lying on a centrosymmetric position and having a similar six-coordinated octahedral structure. One is coordinated by four N atoms from four 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring MnIIcentres to generate a two-dimensional layered structure running parallel to theabplane. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure with3,4,6-ctopology. Thermogravimetric analysis of the title polymer shows that it is stable up to 533 K. The first weight loss between 533 and 573 K corresponds to the release of coordinated ethane-1,2-diol molecules, and further decomposition occurred at 648 K.


2018 ◽  
Vol 74 (4) ◽  
pp. 418-423 ◽  
Author(s):  
Yan-Yan An ◽  
Li-Ping Lu ◽  
Miao-Li Zhu

The design and synthesis of coordination polymers (CPs) have attracted much interest due to the intriguing diversity of their architectures and topologies. The functional solid catena-poly[μ2-aqua-triaqua{μ4-5-[4-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato}{μ3-5-[4-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato}dicobalt(II)], [Co2(C16H10O7)2(H2O)4] n or [Co2(HL)2(μ2-H2O)(H2O)3] n , was synthesized successfully by self-assembly of CoII ions with 5-[(4-carboxyphenoxy)methyl]isophthalic acid (H3 L). The title compound was obtained under hydrothermal conditions and exhibits a twofold interpenetrated three-dimensional skeleton with hms 3,5-conn topology according to the cluster representation for valence-bonded metal–organic frameworks (MOFs). It has been characterized by single-crystal X-ray diffraction, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis and susceptibility measurements. The antiferromagnetic coupling between adjacent CoII centres occurs via superexchange through the ligands.


2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4'-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2'-bipyridine-5,5'-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br><br>


Author(s):  
Zaoming Wang ◽  
Gavin A. Craig ◽  
Alexandre Legrand ◽  
Frederik Haase ◽  
Saori Minami ◽  
...  
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ACS Omega ◽  
2021 ◽  
Author(s):  
Juan M. Garcia-Garfido ◽  
Javier Enríquez ◽  
Ignacio Chi-Durán ◽  
Iván Jara ◽  
Leonardo Vivas ◽  
...  

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