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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Cited by 4 publications

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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Investigation of Supramolecular Self-Assembly in Sn(IV)-5,10,15,20-tetra(4-bromo-2,6-difluorophenyl) Porphyrins Mediated through Activated Sigma Hole

Bandaru,

Singh,

Titi

et al. 2024

Crystal Growth & Design

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The article presents the design, synthesis, characterization, and investigation of halogen-bonding interactions in a series of six-coordinated Sn(IV) complexes based on 5,10,15,20-tetra(4-bromophenyl) porphyrin [Sn(IV)TBrPr] and 5,10,15,20-tetra(4-bromo-2,6-difluoro phenyl) porphyrin [Sn(IV)TBrFPr] with symmetrical axial linkers 3,5-dibromobenzoic acid (3,5-DiBrBA) and 4-bromobenzoic acid (4-BrBA) and nonsymmetrical axial linker 5-bromo nicotinic acid (5-BrNA). Four compounds, namely, Sn(5-BrNA)2(TBrPr) (1), Sn(5-BrNA)2(TBrFPr)·2DMF (2), Sn(3,5-DiBrBA)2(TBrFPr) (3), Sn(4-BrBA)2(TBrFPr) (4), were synthesized and characterized by single-crystal X-ray crystallography. All of the compounds were characterized by 1H NMR, UV–vis absorption, emission, scanning electron microscopy, and cyclic voltammetry. Diverse supramolecular interactions involving bromine and fluorine atoms like Br···Br, Br···F, Br···π, and F···F are successfully manifested in our systems. The single-crystal analysis reveals that the self-assembly in compound 3 displays the shortest type II Br···Br contact of 3.401(3) Å in the realm of porphyrin assemblies, which leads to the formation of a porphyrin dimer. An interesting example of the shortest Br···F contact of 2.937(2) Å is found in compound 4, which facilitates the formation of 3D supramolecular architecture with well-defined hexagonal voids. The shortest contacts observed in our systems are persuaded by the cooperative interactions of the bromine atoms and by the most electron-withdrawing fluorine atoms on the porphyrin skeleton. Electrostatic potential surface analyses show that the σ-hole potential in the bromine atoms is increased by 6.5 kcal by the fluorine atoms. Optical and electrochemical studies detail the electronic structure of the title compounds under the influence of fluorine atoms and axial linkers, while theoretical studies were conducted to calculate the highest occupied molecular orbital–least unoccupied molecular orbital gap to relate with the experimental values.

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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 4 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

Investigation of Supramolecular Self-Assembly in Sn(IV)-5,10,15,20-tetra(4-bromo-2,6-difluorophenyl) Porphyrins Mediated through Activated Sigma Hole

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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 4 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

Investigation of Supramolecular Self-Assembly in Sn(IV)-5,10,15,20-tetra(4-bromo-2,6-difluorophenyl) Porphyrins Mediated through Activated Sigma Hole

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