Applying the Influence of Conformational Freedom on the Network Topologies Showing Impressive Proton Conductivity

De, Avik; Basu, Olivia; Basu, Tannistha; Mondal, Raju

doi:10.1021/acs.cgd.0c01042

Cited by 10 publications

(7 citation statements)

References 114 publications

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“…The hopping mechanism involves the formation of protons which, as the name suggests, subsequently hop from one site to another site with a few local rearrangements. In the second mechanism, protons combine with proton-carrier solvent molecules and vehicles like H 2 O or NH 3 assist the movement through diffusion. − …”

Section: Resultsmentioning

confidence: 99%

A Silver-Based Integrated System Showing Mutually Inclusive Super Protonic Conductivity and Photoswitching Behavior

et al. 2023

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Photoinduced electricity and proton conductivity led fuel cells have emerged, inter alia, as highly promising systems for unconventional energy harvesting. Notwithstanding their individual presence with widely acclaimed results, an integrating system with mutually inclusive manifestation of both features has hitherto not been reported in the literature. To achieve this objective, our approach was to design a ligand system incorporating prerequisite features of both systems, like extended conjugation instigating photophysical activity and functional groups facilitating ionic conduction. As such, we report herein the design, synthesis, and characterization of a pyridyl-pyrazole-based silver compound that exhibits an excellent photocurrent generation and very high proton conductivity. The X-ray single-crystal structure of the Ag complex fully supports our notion, showing extensive π–π conjugated aromatic rings with a protruding free sulfonic group, facing toward solvent-filled channels with numerous supramolecular interactions. The nanoscopic silver metallogel induces semiconductive features in the system which ultimately result in photoresponse behavior in terms of photocurrent generation with an whopping photocurrent gain (I on/I off) of 21.2. To complete the idea of an integrated system, the proton conductivity values were also measured for both gel and crystalline states, while the former state yields a better result. The maximum proton conductivity value turns out to be 1.03 × 10–2 S cm–1 at 70 °C, which is higher than or comparable to those of well-known systems in the literature for proton conductivity.

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Section: Resultsmentioning

confidence: 99%

A Silver-Based Integrated System Showing Mutually Inclusive Super Protonic Conductivity and Photoswitching Behavior

et al. 2023

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“…24 Our recent studies on MOFs, often containing porous channels filled with extensive hydrogen-bonded protic solvents, based on a flexible bispyrazole-based ligand, methylenebis(3,5-dimethylpyrazole) (H 2 MDP) showing interesting magnetic and electrical properties, inspired us to further explore this subject. 25 As such, we report herein the synthesis, structural analysis, and electrical and magnetic properties of two multifunctional MOFs…”

Section: ■ Introductionmentioning

confidence: 99%

“…The basic prerequisites for inducing magnetic-electrical properties would be generating paramagnetic metal based MOFs with ligand containing functional groups that can facilitate charge activation as well as boosting the charge mobility, preferably through extended hydrogen bonded network . Our recent studies on MOFs, often containing porous channels filled with extensive hydrogen-bonded protic solvents, based on a flexible bispyrazole-based ligand, methylenebis(3,5-dimethylpyrazole) (H 2 MDP) showing interesting magnetic and electrical properties, inspired us to further explore this subject …”

Section: Introductionmentioning

confidence: 99%

Magnetic and Electric Properties of Pyrazole-Based Metal–Organic Frameworks Grafted With a Sulfonic Moiety

Saha

Das

et al. 2023

Crystal Growth & Design

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We report herein two multifunctional metal–organic frameworks (MOFs) that exhibit excellent mutually inclusive electrical and magnetic properties. Accordingly, two cobalt and nickel based MOFs (Co-MOF, Ni-MOF) were generated using a flexible bispyrazole based ligand and 2-sulphono terephthalic acid. The idea is to generate paramagnetic metal ion based magnetic MOFs, which can also be used to fabricate electrical devices by utilizing the immobilized free sulfonic groups and encapsulated H-bonded water clusters for active charge species generation and transportation. Further support comes from the intriguing structural features of the MOFs that include extensive H-bonded water clusters, free sulfonic acid moiety, or syn-anti bridged carboxylates, which make them highly suitable candidates for generating electrical and magnetic materials. Further complementary support for their candidature comes from the high thermal, chemical, and physical stability of the MOFs. The impedance spectroscopy data and I–V results unequivocally support the suitability of the MOFs for electronic device fabrication showing a befitting conductivity value of 1.80 × 10–4 S/m with an ideality factor of 1.06 for Ni-MOF. Interestingly, the Co-MOF shows a light-dependent behavior with conductivity values of 9.09 × 10–5 S/m (dark) and 6.31 × 10–4 S/m (light) and ideality factors of 0.78 (dark) and 0.92 (light). The MOFs, fitted with a free sulfonic acid moiety and extensive H-bonded water clusters, show high potential for proton exchange membrane fuel cells (PEMFCs) development with corroborating proton conductivity values of 1.95× 10–3 S/cm and 5.80 × 10–4 S/cm for Ni-MOF and Co-MOF, respectively, at 95% relative humidity and 85 °C. Moreover, the interesting structural aspects like syn-anti bridged carboxylates prompt us to explore the magnetic behavior of the MOFs. The Ni-MOF shows some interesting antiferromagnetic behavior. The Co-MOF reveals intriguing single molecule magnet behavior with a U eff value of 34 K and moderate relaxation time of 3.5× 10–8 s.

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“…As a new type of crystalline material, MOFs have received extensive attention mainly due to their fascinating morphology and tunable surface properties realized by judiciously choosing metal ions and organic ligands modified with appropriate functional groups. 1,2 They have been widely used in the field of gas adsorption, 3 drug delivery, 4 luminescence sensing, [5][6][7][8][9][10][11][12] proton conduction, [13][14][15][16][17][18] etc. MOFs provide an infinite array of metal ion centers and connecting ligands, which may be redox active or inactive.…”

Section: Introductionmentioning

confidence: 99%

Preparation, characterization, and electrochemical sensing performance of a novel pristine Cd-MOF and its composite with carbon nanotubes

2023

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Applying the Influence of Conformational Freedom on the Network Topologies Showing Impressive Proton Conductivity

Cited by 10 publications

References 114 publications

A Silver-Based Integrated System Showing Mutually Inclusive Super Protonic Conductivity and Photoswitching Behavior

A Silver-Based Integrated System Showing Mutually Inclusive Super Protonic Conductivity and Photoswitching Behavior

Magnetic and Electric Properties of Pyrazole-Based Metal–Organic Frameworks Grafted With a Sulfonic Moiety

Preparation, characterization, and electrochemical sensing performance of a novel pristine Cd-MOF and its composite with carbon nanotubes

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