Noncovalent interaction guided selectivity of haloaromatic isomers in a flexible porous coordination polymer

Jena, Rohan; Laha, Subhajit; Dwarkanath, Nimish; Hazra, Arpan; Haldar, Ritesh; Balasubramanian, Sundaram; Maji, Tapas Kumar

doi:10.1039/d3sc03079b

Chem. Sci.

2023

DOI: 10.1039/d3sc03079b

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Noncovalent interaction guided selectivity of haloaromatic isomers in a flexible porous coordination polymer

Rohan Jena,

Subhajit Laha,

Nimish Dwarkanath

et al.

Abstract: Porous, supramolecular structures exhibit preferential encapsulation of guest molecules, primarily by the means of differences in the order of (noncovalent) interactions. The encapsulation preferences can be for geometry (dimension and...

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References 60 publications

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Electron Rich Guest Regulated Enhanced CO₂ Reduction in a Multivariate Porous Coordination Polymer

Jena,

Rahimi,

Karmakar

et al. 2024

Adv Funct Materials

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The need for carbon‐neutralization technologies has prompted significant interest in developing materials for CO2 reduction. Donor–acceptor (D–A) based flexible porous coordination polymers {[Zn(o‐phen)(ndc)].(guest)}n, (guest = anthracene = 1‐Ant, and pyrene = 1‐Pyr) are reported as photocatalysts for CO2RR, yielding higher order CH4 product. Electron‐rich anthracene (Ant) and pyrene (Pyr) guests are confined within nanopores, forming D–A charge transfer (CT) complexes with o‐phen ligand of the host. CT interaction enhances visible light absorption and modulates excitonic properties of the photocatalyst by electronic push‐pull effect (exciton binding energy 87 meV for 1‐Ant and 104 meV for 1‐Pyr). Electron donation capability varies from Pyr to Ant, affecting catalytic properties; 1‐Ant yields 1.24 mmolg−1 of CH4 (0.47 mmolg−1 for 1‐Pyr) with CO as minor product. A mixed‐metal multivariate PCP {[Zn0.55Co0.45(o‐phen)(ndc)].(Ant)}n, (1′‐Ant) prepared based on solid‐solution approach by substituting Zn(II) with redox‐active Co(II) enhances CH4 production (2.79 mmolg−1, ≈94% selectivity). D–A CT complex harvests visible light and channels electrons to Co(II) for CO2RR. In situ DRIFTS and theoretical studies elucidate Co(II) site's role in CO2 binding and stabilizing reaction intermediates. This work underscores guest‐modulated electron transfer in PCPs for tailoring catalytic properties by introducing a redox‐active metal in a multivariate approach.

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Electron Rich Guest Regulated Enhanced CO₂ Reduction in a Multivariate Porous Coordination Polymer

Jena,

Rahimi,

Karmakar

et al. 2024

Adv Funct Materials

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Efficient adsorptive separation of nitrotoluene isomers via a stable and low-cost metal–organic framework with descending affinity order of meta-/ortho-/para-isomers

Zhang,

Huang,

Huang

et al. 2025

Separation and Purification Technology

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Noncovalent interaction guided selectivity of haloaromatic isomers in a flexible porous coordination polymer

Abstract: Porous, supramolecular structures exhibit preferential encapsulation of guest molecules, primarily by the means of differences in the order of (noncovalent) interactions. The encapsulation preferences can be for geometry (dimension and...

Cited by 2 publications

References 60 publications

Electron Rich Guest Regulated Enhanced CO₂ Reduction in a Multivariate Porous Coordination Polymer

Electron Rich Guest Regulated Enhanced CO₂ Reduction in a Multivariate Porous Coordination Polymer

Efficient adsorptive separation of nitrotoluene isomers via a stable and low-cost metal–organic framework with descending affinity order of meta-/ortho-/para-isomers

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About

Noncovalent interaction guided selectivity of haloaromatic isomers in a flexible porous coordination polymer

Abstract: Porous, supramolecular structures exhibit preferential encapsulation of guest molecules, primarily by the means of differences in the order of (noncovalent) interactions. The encapsulation preferences can be for geometry (dimension and...

Cited by 2 publications

References 60 publications

Electron Rich Guest Regulated Enhanced CO2 Reduction in a Multivariate Porous Coordination Polymer

Electron Rich Guest Regulated Enhanced CO2 Reduction in a Multivariate Porous Coordination Polymer

Efficient adsorptive separation of nitrotoluene isomers via a stable and low-cost metal–organic framework with descending affinity order of meta-/ortho-/para-isomers

Contact Info

Product

Resources

About

Electron Rich Guest Regulated Enhanced CO₂ Reduction in a Multivariate Porous Coordination Polymer

Electron Rich Guest Regulated Enhanced CO₂ Reduction in a Multivariate Porous Coordination Polymer