scholarly journals Pore-controlled formation of 0D metal complexes in anionic 3D metal–organic frameworks

CrystEngComm ◽  
2015 ◽  
Vol 17 (5) ◽  
pp. 996-1000 ◽  
Author(s):  
Muwei Zhang ◽  
Mathieu Bosch ◽  
Hong-Cai Zhou

The host–guest chemistry between a series of anionic MOFs and their trapped counterions was investigated by single crystal XRD.

2019 ◽  
Author(s):  
javier enriquez ◽  
Ignacio Chi-Duran ◽  
Carolina Manquian ◽  
Felipe Herrera ◽  
Ruben Fritz ◽  
...  

Non-centrosymmetric single-crystal metal-organic frameworks (MOF) are promising candidates for phase-matched nonlinear optical communication, but typical hydrothermal synthesis produces small crystals with relatively low transmittance and poor phase matching. We study the effect of the metal-to-ligand molar ratio and reaction pH on the hydro-thermal synthesis of the non-centrosymmetric Zn(3-ptz)<sub>2</sub> and Zn(OH)(3-ptz) MOFs with <i>in-situ </i>ligand formation. In acidic environments, we find that decreasing the amount of ligand below the stoichiometric molar ratio 1:2 also produces highly transparent single-crystal octahedrons of <b>Zn(3-ptz)<sub>2</sub></b>. In alkaline environments, we obtain long rod-like <b>Zn(OH)(3-ptz) </b>crystals whose length exceeds previous reports by up to four orders of magnitude. Potential applications of these results in the development of MOF-based nonlinear optical devices are discussed.


2021 ◽  
Vol 9 (15) ◽  
pp. 5082-5087
Author(s):  
Yu Gong ◽  
Wang-Kang Han ◽  
Hui-Shu Lu ◽  
Qing-Tao Hu ◽  
Huan Tu ◽  
...  

New Hofmann-type metal–organic frameworks display rare and complete ligand exchange induced single crystal to single crystal transformations from 3D frameworks to 2D layers, accompanied by magnetic properties transition from two-step SCO behavior to hysteretic SCO behavior.


2021 ◽  
Author(s):  
Qing-Xia Yao ◽  
Miaomiao Tian ◽  
Jun Zheng ◽  
Jintang Xue ◽  
Xuze Pan ◽  
...  

A series of microporous Ln(III)-based metal-organic frameworks (1-Ln) have been hydrothermally synthesized by using 4,4',4''-nitrilotribenzoic acid (H3NTB). Single crystal X-ray diffraction analyses show 1-Ln are isostructural and have 3D porous...


Author(s):  
Michael T. Huxley ◽  
Campbell J. Coghlan ◽  
Witold M. Bloch ◽  
Alexandre Burgun ◽  
Christian J. Doonan ◽  
...  

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.


2012 ◽  
Vol 12 (6) ◽  
pp. 3243-3249 ◽  
Author(s):  
Mikaela Gustafsson ◽  
Jie Su ◽  
Huijuan Yue ◽  
Qingxia Yao ◽  
Xiaodong Zou

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