Controlling the Alignment of 1D Nanochannel Arrays in Oriented Metal-Organic Framework Films for Host-Guest Materials Design

Here, we successfully prepared macroscopically oriented films of Cu-based pillar-layered MOFs (Cu2(Linker)2DABCO) having regularly ordered 1D nanochannels. The direction of 1D nanochannels was controllable by optimizing the crystal growth process; 1D nanochannels either perpendicular or parallel to substrates, which offer molecular-scale pore arrays for a macroscopic alignment of functional guest molecules in the desired direction. We also showed the fabrication of oriented Cu2(Linker)2DABCO MOF patterns, where the direction of 1D nanochannels is controllable on individual locations on the same substrate. These Cu2(Linker)2DABCO MOF films and patterns with controlled orientation are importante steps towards the development of MOF film-based applications such as sensors and electrical/optical devices because functionalities derived from the accommodated guest species in their 1D nanochannels are optimized for the rational direction on the desired substrate for the device fabrication.

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Synthesis and Structure of a Clathrated Two-Dimensional Metal-Organic Framework: [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2·H2O (L = Bis(1-pyrazinylethylidene)hydrazine)

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20080024 ◽

2008 ◽

Vol 73 (1) ◽

pp. 24-31

Author(s):

Dayu Wu ◽

Genhua Wu ◽

Wei Huang ◽

Zhuqing Wang

Keyword(s):

Metal Organic Framework ◽

Channel Structure ◽

Two Dimensional ◽

X Ray Diffraction ◽

Guest Molecules ◽

X Ray ◽

Square Planar ◽

Metal Organic ◽

Aqueous Meoh ◽

Organic Framework

The compound [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2 was obtained by the reaction of Cd(ClO4)2, bis(1-pyrazinylethylidene)hydrazine (L) and 4,4'-bipyridine in aqueous MeOH. Single-crystal X-ray diffraction has revealed its two-dimensional metal-organic framework. The 2-D layers superpose on each other, giving a channel structure. The square planar grids consist of two pairs of shared edges with Cd(II) ion and a 4,4'-bipyridine molecule each vertex and side, respectively. The square cavity has a dimension of 11.817 × 11.781 Å. Two guest molecules of bis(1-pyrazinylethylidene)hydrazine are clathrated in every hydrophobic host cavity, being further stabilized by π-π stacking and hydrogen bonding. The results suggest that the hydrazine molecules present in the network serve as structure-directing templates in the formation of crystal structures.

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Metal-Organic Framework-Based Stimuli-Responsive Polymers

Journal of Composites Science ◽

10.3390/jcs5040101 ◽

2021 ◽

Vol 5 (4) ◽

pp. 101

Author(s):

Menglian Wei ◽

Yu Wan ◽

Xueji Zhang

Keyword(s):

Metal Organic Framework ◽

Chemical Properties ◽

Stimuli Responsive ◽

Guest Molecules ◽

Stimuli Responsive Polymers ◽

Responsive Polymers ◽

Reversible Phase Transition ◽

Metal Organic ◽

External Stimuli ◽

Organic Framework

Metal-organic framework (MOF) based stimuli-responsive polymers (coordination polymers) exhibit reversible phase-transition behavior and demonstrate attractive properties that are capable of altering physical and/or chemical properties upon exposure to external stimuli, including pH, temperature, ions, etc., in a dynamic fashion. Thus, their conformational change can be imitated by the adsorption/desorption of target analytes (guest molecules), temperature or pressure changes, and electromagnetic field manipulation. MOF-based stimuli responsive polymers have received great attention due to their advanced optical properties and variety of applications. Herein, we summarized some recent progress on MOF-based stimuli-responsive polymers (SRPs) classified by physical and chemical responsiveness, including temperature, pressure, electricity, pH, metal ions, gases, alcohol and multi-targets.

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Photofunctional metal-organic framework thin films for sensing, catalysis and device fabrication

Inorganica Chimica Acta ◽

10.1016/j.ica.2020.119926 ◽

2020 ◽

Vol 513 ◽

pp. 119926 ◽

Cited By ~ 1

Author(s):

Germán E. Gomez ◽

Federico Roncaroli

Keyword(s):

Thin Films ◽

Metal Organic Framework ◽

Device Fabrication ◽

Metal Organic ◽

Organic Framework

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Solvent exchange in a metal–organic framework single crystal monitored by dynamicin situX-ray diffraction

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520617008447 ◽

2017 ◽

Vol 73 (4) ◽

pp. 669-674 ◽

Cited By ~ 5

Author(s):

Jordan M. Cox ◽

Ian M. Walton ◽

Gage Bateman ◽

Cassidy A. Benson ◽

Travis Mitchell ◽

...

Keyword(s):

Rational Design ◽

Metal Organic Framework ◽

X Ray Diffraction ◽

Guest Molecules ◽

Time Resolved ◽

Ethanol Solvate ◽

Significant Step ◽

Metal Organic ◽

Flexible Metal ◽

Organic Framework

Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamicin situX-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal–organic framework [Co(AIP)(bpy)0.5(H2O)]·2H2O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.

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Metal–organic framework tethering pH- and thermo-responsive polymer for ON–OFF controlled release of guest molecules

CrystEngComm ◽

10.1039/c9ce01731c ◽

2020 ◽

Vol 22 (6) ◽

pp. 1106-1111

Author(s):

Shunjiro Nagata ◽

Kenta Kokado ◽

Kazuki Sada

Keyword(s):

Controlled Release ◽

Metal Organic Framework ◽

Guest Molecules ◽

Responsive Polymer ◽

Metal Organic ◽

Organic Framework

Metal–organic framework tethering pH- and thermo-responsive polymer underwent ON–OFF controlled release of the included guest molecules.

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Dynamics and disposition of benzene guest molecules in the micropore channels of a flexible metal-organic framework studied by 2H NMR and X-ray crystallography

Microporous and Mesoporous Materials ◽

10.1016/j.micromeso.2003.11.020 ◽

2004 ◽

Vol 73 (1-2) ◽

pp. 71-79 ◽

Cited By ~ 20

Author(s):

C.I. Ratcliffe ◽

D.V. Soldatov ◽

J.A. Ripmeester

Keyword(s):

Metal Organic Framework ◽

2H Nmr ◽

Guest Molecules ◽

X Ray ◽

X Ray Crystallography ◽

Metal Organic ◽

Flexible Metal ◽

Organic Framework

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Dynamic Topochemical Reaction Tuned by Guest Molecules in the Nanospace of a Metal–Organic Framework

Journal of the American Chemical Society ◽

10.1021/jacs.9b07682 ◽

2019 ◽

Vol 141 (40) ◽

pp. 15742-15746 ◽

Cited By ~ 16

Author(s):

Shinpei Kusaka ◽

Atsushi Kiyose ◽

Hiroshi Sato ◽

Yuh Hijikata ◽

Akihiro Hori ◽

...

Keyword(s):

Metal Organic Framework ◽

Topochemical Reaction ◽

Guest Molecules ◽

Metal Organic ◽

Organic Framework

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Detection of Adsorbates on Emissive MOF Surfaces with X-Ray Photoelectron Spectroscopy

10.26434/chemrxiv.7210409 ◽

2018 ◽

Author(s):

Shawn Burdette ◽

Jingjing Yan ◽

Ron Grimm ◽

Peter Mueller ◽

Alexander Carl ◽

...

Keyword(s):

Photoelectron Spectroscopy ◽

Analytical Approach ◽

Metal Organic Framework ◽

Model System ◽

Guest Molecules ◽

X Ray ◽

Phenol Derivatives ◽

Metal Organic ◽

Azobenzene Chromophore ◽

Organic Framework

A metal organic framework containing an azobenzene chromophore exhibits luminescence that is quenched by nitro-phenol derivatives. The model system was used to develop an new analytical approach to differentiating between encapsulated guest molecules and those adsorbed on the outside of the MOF

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A Three-Dimensional Metal-Organic Framework Displaying Guest-Dependent Spin-Crossover Behaviour

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.779.110 ◽

2018 ◽

Vol 779 ◽

pp. 110-114

Author(s):

Feng Shao ◽

Jia Jia Zhuang ◽

Gang Luo ◽

Ke Zhang ◽

Chang Jiang Li ◽

...

Keyword(s):

Spin Crossover ◽

Metal Organic Framework ◽

Three Dimensional ◽

Organic Complex ◽

Single Crystal Diffraction ◽

Guest Molecules ◽

X Ray ◽

Metal Organic Complex ◽

Metal Organic ◽

3D Framework

A new three-dimensional metal-organic complex, [{Fe (NCSe)2}3(TPB)4]x(guest), was prepared with the ligand of TPB (1,3,5-tris (4-pyridyl) benzene). The X-ray single crystal diffraction studied in 100 K and 173 K shown the change of bonds and angles of the framework. The guest exchange and magnetic properties indicated that the 3D framework can be responsible to the solvent guest molecules and shows guest-dependent spin-crossover behaviour.

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