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Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer

This article reports alternating supramolecular copolymerization of two naphthalene-diimide (NDI)-derived building blocks (NDI-1 and NDI-2) under thermodynamic control. Both monomers contain a central NDI chromophore, attached to a hydrocarbon-chain and a carboxylic-acid group. The NDI core in NDI-2...

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Autores principales: Chakraborty, Anwesha, Das, Pradipta Kumar, Jana, Biman, Ghosh, Suhrit
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10566455/
https://www.ncbi.nlm.nih.gov/pubmed/37829017
http://dx.doi.org/10.1039/d3sc03056c
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author Chakraborty, Anwesha
Das, Pradipta Kumar
Jana, Biman
Ghosh, Suhrit
author_facet Chakraborty, Anwesha
Das, Pradipta Kumar
Jana, Biman
Ghosh, Suhrit
author_sort Chakraborty, Anwesha
collection PubMed
description This article reports alternating supramolecular copolymerization of two naphthalene-diimide (NDI)-derived building blocks (NDI-1 and NDI-2) under thermodynamic control. Both monomers contain a central NDI chromophore, attached to a hydrocarbon-chain and a carboxylic-acid group. The NDI core in NDI-2 is symmetrically substituted with two butane-thiol groups, which makes it distinct from NDI-1. In decane, a 1 : 1 mixture of NDI-1 and NDI-2 shows spontaneous gelation and a typical fibrillar network, unlike the behavior of either of the components individually. The solvent-dependent UV/vis spectrum of the mixed sample in decane shows bathochromically shifted sharp absorption bands and a sharp emission band (holds a mirror-image relationship) with a significantly small Stokes shift compared to those in CHCl(3), indicating J-aggregation. In contrast, the aggregated spectra of the individual monomers show broad structureless features, suggesting ill-defined aggregates. Cooling curves derived from the temperature-dependent UV/vis spectroscopy studies revealed early nucleation and a signature of well-defined cooperative polymerization for the mixed sample, unlike either of the individual components. Molecular dynamics simulations predicted the greatest dimer formation tendency for the NDI-1 + NDI-2 (1 : 1), followed by pure NDI-1 and NDI-2. Theoretical studies further revealed a partial positive charge in the NDI ring of NDI-1 when compared to NDI-2, promoting the alternating stacking propensity, which is also favored by the steric factor as NDI-2 is core-substituted with alkyl thiols. Such theoretical predictions fully corroborate with the experimental results showing 1 : 1 stoichiometry (from Job's plot) of the two monomers, indicating alternate stacking sequences in the H-bonded (syn–syn catemer type) supramolecular copolymer. Such alternating supramolecular copolymers showed highly efficient (>93%) fluorescence resonance energy transfer (FRET).
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spelling pubmed-105664552023-10-12 Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer Chakraborty, Anwesha Das, Pradipta Kumar Jana, Biman Ghosh, Suhrit Chem Sci Chemistry This article reports alternating supramolecular copolymerization of two naphthalene-diimide (NDI)-derived building blocks (NDI-1 and NDI-2) under thermodynamic control. Both monomers contain a central NDI chromophore, attached to a hydrocarbon-chain and a carboxylic-acid group. The NDI core in NDI-2 is symmetrically substituted with two butane-thiol groups, which makes it distinct from NDI-1. In decane, a 1 : 1 mixture of NDI-1 and NDI-2 shows spontaneous gelation and a typical fibrillar network, unlike the behavior of either of the components individually. The solvent-dependent UV/vis spectrum of the mixed sample in decane shows bathochromically shifted sharp absorption bands and a sharp emission band (holds a mirror-image relationship) with a significantly small Stokes shift compared to those in CHCl(3), indicating J-aggregation. In contrast, the aggregated spectra of the individual monomers show broad structureless features, suggesting ill-defined aggregates. Cooling curves derived from the temperature-dependent UV/vis spectroscopy studies revealed early nucleation and a signature of well-defined cooperative polymerization for the mixed sample, unlike either of the individual components. Molecular dynamics simulations predicted the greatest dimer formation tendency for the NDI-1 + NDI-2 (1 : 1), followed by pure NDI-1 and NDI-2. Theoretical studies further revealed a partial positive charge in the NDI ring of NDI-1 when compared to NDI-2, promoting the alternating stacking propensity, which is also favored by the steric factor as NDI-2 is core-substituted with alkyl thiols. Such theoretical predictions fully corroborate with the experimental results showing 1 : 1 stoichiometry (from Job's plot) of the two monomers, indicating alternate stacking sequences in the H-bonded (syn–syn catemer type) supramolecular copolymer. Such alternating supramolecular copolymers showed highly efficient (>93%) fluorescence resonance energy transfer (FRET). The Royal Society of Chemistry 2023-09-19 /pmc/articles/PMC10566455/ /pubmed/37829017 http://dx.doi.org/10.1039/d3sc03056c Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Chakraborty, Anwesha
Das, Pradipta Kumar
Jana, Biman
Ghosh, Suhrit
Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer
title Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer
title_full Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer
title_fullStr Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer
title_full_unstemmed Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer
title_short Supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer
title_sort supramolecular alternating copolymers with highly efficient fluorescence resonance energy transfer
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10566455/
https://www.ncbi.nlm.nih.gov/pubmed/37829017
http://dx.doi.org/10.1039/d3sc03056c
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AT ghoshsuhrit supramolecularalternatingcopolymerswithhighlyefficientfluorescenceresonanceenergytransfer