scholarly journals Isoreticular Linker Substitution in Conductive Metal–Organic Frameworks with Through‐Space Transport Pathways

2020 ◽  
Vol 59 (44) ◽  
pp. 19623-19626 ◽  
Author(s):  
Lilia S. Xie ◽  
Sarah S. Park ◽  
Michał J. Chmielewski ◽  
Hanyu Liu ◽  
Ruby A. Kharod ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Transport Pathways ◽  
Metal Organic

scholarly journals Strategies for Controlling Through-Space Charge Transport in Metal-Organic Frameworks via Structural Modifications

Nanomaterials ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 2372
Author(s):  
Christian Winkler ◽  
Egbert Zojer
Keyword(s):  
Space Charge ◽  
Charge Transport ◽  
Density Functional ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Structural Defects ◽  
Transport Pathways ◽  
Metal Organic ◽  
The Individual ◽  
The Impact

In recent years, charge transport in metal-organic frameworks (MOFs) has shifted into the focus of scientific research. In this context, systems with efficient through-space charge transport pathways resulting from π-stacked conjugated linkers are of particular interest. In the current manuscript, we use density functional theory-based simulations to provide a detailed understanding of such MOFs, which, in the present case, are derived from the prototypical Zn2(TTFTB) system (with TTFTB4− corresponding to tetrathiafulvalene tetrabenzoate). In particular, we show that factors such as the relative arrangement of neighboring linkers and the details of the structural conformations of the individual building blocks have a profound impact on bandwidths and charge transfer. Considering the helical stacking of individual tetrathiafulvalene (TTF) molecules around a screw axis as the dominant symmetry element in Zn2(TTFTB)-derived materials, the focus, here, is primarily on the impact of the relative rotation of neighboring molecules. Not unexpectedly, changing the stacking distance in the helix also plays a distinct role, especially for structures which display large electronic couplings to start with. The presented results provide guidelines for achieving structures with improved electronic couplings. It is, however, also shown that structural defects (especially missing linkers) provide major obstacles to charge transport in the studied, essentially one-dimensional systems. This suggests that especially the sample quality is a decisive factor for ensuring efficient through-space charge transport in MOFs comprising stacked π-systems.

scholarly journals Isoreticular Linker Substitution in Conductive Metal–Organic Frameworks with Through-Space Transport Pathways

2020 ◽  
Author(s):  
Lilia S. Xie ◽  
Sarah S. Park ◽  
Michał J. Chmielewski ◽  
Hanyu Liu ◽  
Ruby A. Kharod ◽  
...  
Keyword(s):  
Charge Transport ◽  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
Strong Interactions ◽  
Conductivity Data ◽  
Electrically Conductive ◽  
Transport Pathways ◽  
Intermolecular Contacts ◽  
Metal Organic

<p>The extension of reticular chemistry concepts to electrically conductive three-dimensional metal-organic frameworks (MOFs) has been challenging, particularly for cases in which strong interactions between electroactive linkers create the charge transport pathways. Here, we report the successful replacement of tetrathiafulvalene (TTF) with a nickel glyoximate core in a family of isostructural conductive MOFs with Mn<sup>2+</sup>, Zn<sup>2+</sup>, and Cd<sup>2+</sup>. Different coordination environments of the framework metals lead to variations in the linker stacking geometries and optical properties. Single crystal conductivity data are consistent with charge transport along the linker stacking direction, with conductivity values only slightly lower than those reported for the analogous TTF materials. These results serve as a case study demonstrating how reticular chemistry design principles can be extended to conductive frameworks with significant intermolecular contacts.</p>

scholarly journals Isoreticular Linker Substitution in Conductive Metal–Organic Frameworks with Through‐Space Transport Pathways

2020 ◽  
Vol 132 (44) ◽  
pp. 19791-19794
Author(s):  
Lilia S. Xie ◽  
Sarah S. Park ◽  
Michał J. Chmielewski ◽  
Hanyu Liu ◽  
Ruby A. Kharod ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Transport Pathways ◽  
Metal Organic

scholarly journals Isoreticular Linker Substitution in Conductive Metal–Organic Frameworks with Through-Space Transport Pathways

2020 ◽  
Author(s):  
Lilia S. Xie ◽  
Sarah S. Park ◽  
Michał J. Chmielewski ◽  
Hanyu Liu ◽  
Ruby A. Kharod ◽  
...  
Keyword(s):  
Charge Transport ◽  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
Strong Interactions ◽  
Conductivity Data ◽  
Electrically Conductive ◽  
Transport Pathways ◽  
Intermolecular Contacts ◽  
Metal Organic

<p>The extension of reticular chemistry concepts to electrically conductive three-dimensional metal-organic frameworks (MOFs) has been challenging, particularly for cases in which strong interactions between electroactive linkers create the charge transport pathways. Here, we report the successful replacement of tetrathiafulvalene (TTF) with a nickel glyoximate core in a family of isostructural conductive MOFs with Mn<sup>2+</sup>, Zn<sup>2+</sup>, and Cd<sup>2+</sup>. Different coordination environments of the framework metals lead to variations in the linker stacking geometries and optical properties. Single crystal conductivity data are consistent with charge transport along the linker stacking direction, with conductivity values only slightly lower than those reported for the analogous TTF materials. These results serve as a case study demonstrating how reticular chemistry design principles can be extended to conductive frameworks with significant intermolecular contacts.</p>

Metal-Organic Frameworks

2021 ◽  
Author(s):  
Lars Öhrström ◽  
Francoise M. Amombo Noa
Keyword(s):  
Metal Organic Frameworks ◽  
Metal Organic

Substrate templated synthesis of single-phase and uniform Zr-porphyrin-based metal–organic frameworks

2020 ◽  
Vol 7 (1) ◽  
pp. 221-231
Author(s):  
Seong Won Hong ◽  
Ju Won Paik ◽  
Dongju Seo ◽  
Jae-Min Oh ◽  
Young Kyu Jeong ◽  
...  
Keyword(s):  
Chemical Bath Deposition ◽  
Single Phase ◽  
Metal Organic Frameworks ◽  
Templated Synthesis ◽  
Pore Structures ◽  
Phase Pure ◽  
Metal Organic ◽  
Cbd Method

We successfully demonstrate that the chemical bath deposition (CBD) method is a versatile method for synthesizing phase-pure and uniform MOFs by controlling their nucleation stages and pore structures.

Sign in / Sign up

Export Citation Format

Share Document