Physical properties of porphyrin-based crystalline metal‒organic frameworks

AbstractMetal‒organic frameworks (MOFs) are widely studied molecular assemblies that have demonstrated promise for a range of potential applications. Given the unique and well-established photophysical and electrochemical properties of porphyrins, porphyrin-based MOFs are emerging as promising candidates for energy harvesting and conversion applications. Here we discuss the physical properties of porphyrin-based MOFs, highlighting the evolution of various optical and electronic features as a function of their modular framework structures and compositional variations.

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Controlled Growth of the Non-centrosymmetric Zn(3-ptz)2 and Zn(Oh)(3-ptz) Metal-organic Frameworks

10.26434/chemrxiv.7588640.v1 ◽

2019 ◽

Author(s):

javier enriquez ◽

Ignacio Chi-Duran ◽

Carolina Manquian ◽

Felipe Herrera ◽

Ruben Fritz ◽

...

Keyword(s):

Single Crystal ◽

Nonlinear Optical ◽

Metal Organic Frameworks ◽

Molar Ratio ◽

Thermal Synthesis ◽

Small Crystals ◽

Alkaline Environments ◽

Potential Applications ◽

Metal Organic ◽

Long Rod

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)2 and Zn(OH)(3-ptz) MOFs with in-situ 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 Zn(3-ptz)2. In alkaline environments, we obtain long rod-like Zn(OH)(3-ptz) 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.

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Exciton Coupling and Conformational Changes Impacting the Excited State Properties of Metal Organic Frameworks

Molecules ◽

10.3390/molecules25184230 ◽

2020 ◽

Vol 25 (18) ◽

pp. 4230

Author(s):

Andreas Windischbacher ◽

Luca Steiner ◽

Ritesh Haldar ◽

Christof Wöll ◽

Egbert Zojer ◽

...

Keyword(s):

Conformational Changes ◽

Photophysical Properties ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

Red Shift ◽

Light Emitting ◽

Light Emitting Devices ◽

Exciton Coupling ◽

Metal Organic ◽

Crystalline Metal

In recent years, the photophysical properties of crystalline metal-organic frameworks (MOFs) have become increasingly relevant for their potential application in light-emitting devices, photovoltaics, nonlinear optics and sensing. The availability of high-quality experimental data for such systems makes them ideally suited for a validation of quantum mechanical simulations, aiming at an in-depth atomistic understanding of photophysical phenomena. Here we present a computational DFT study of the absorption and emission characteristics of a Zn-based surface-anchored metal-organic framework (Zn-SURMOF-2) containing anthracenedibenzoic acid (ADB) as linker. Combining band-structure and cluster-based simulations on ADB chromophores in various conformations and aggregation states, we are able to provide a detailed explanation of the experimentally observed photophysical properties of Zn-ADB SURMOF-2: The unexpected (weak) red-shift of the absorption maxima upon incorporating ADB chromophores into SURMOF-2 can be explained by a combination of excitonic coupling effects with conformational changes of the chromophores already in their ground state. As far as the unusually large red-shift of the emission of Zn-ADB SURMOF-2 is concerned, based on our simulations, we attribute it to a modification of the exciton coupling compared to conventional H-aggregates, which results from a relative slip of the centers of neighboring chromophores upon incorporation in Zn-ADB SURMOF-2.

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Synthesis, designing strategies and photocatalytic charge dynamics of Metal-Organic Frameworks (MOFs): A catalyzed Photo-degradation approach towards Organic Dyes

Catalysis Science & Technology ◽

10.1039/d0cy02275f ◽

2021 ◽

Author(s):

Ayushi Singh ◽

Ashish Kumar Singh ◽

Jian-Qiang Liu ◽

Abhinav Kumar

Keyword(s):

Small Molecule ◽

Coordination Polymers ◽

Organic Dyes ◽

Metal Organic Frameworks ◽

Gas Storage ◽

New Variety ◽

Photo Degradation ◽

Charge Dynamics ◽

Potential Applications ◽

Metal Organic

Metal-organic frameworks (MOFs) or coordination polymers (CPs) are regarded as new variety of materials that find potential applications in plethora of areas such as gas/small molecule absorption/separation, gas storage, membranes...

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Potential applications of metal-organic frameworks

Coordination Chemistry Reviews ◽

10.1016/j.ccr.2009.05.019 ◽

2009 ◽

Vol 253 (23-24) ◽

pp. 3042-3066 ◽

Cited By ~ 1104

Author(s):

Ryan J. Kuppler ◽

Daren J. Timmons ◽

Qian-Rong Fang ◽

Jian-Rong Li ◽

Trevor A. Makal ◽

...

Keyword(s):

Metal Organic Frameworks ◽

Potential Applications ◽

Metal Organic

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Lanthanide metal–organic frameworks based on the 4,4′-oxybisbenzoic acid ligand: synthesis, structures and physical properties

New Journal of Chemistry ◽

10.1039/c5nj01930c ◽

2015 ◽

Vol 39 (12) ◽

pp. 9872-9878 ◽

Cited By ~ 5

Author(s):

Yun Li ◽

Ning Wang ◽

Yan-Ju Xiong ◽

Qian Cheng ◽

Jie-Fang Fang ◽

...

Keyword(s):

Physical Properties ◽

Solvothermal Synthesis ◽

Metal Organic Frameworks ◽

Lanthanide Ions ◽

Acid Ligand ◽

Metal Organic ◽

Lanthanide Metal ◽

Ligand Synthesis

Using solvothermal synthesis, eight new 3D microporous lanthanide-ions-based MOFs constructed from 4,4′-oxybisbenzoic acid were obtained and displayed two types of architecture.

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