σ‐Electrons Responsible for Cooperativity and Ring Equalization in Hydrogen‐Bonded Supramolecular Polymers
ChemPlusChem, vol. 87, pp. e202100436
Abstract
We have quantum chemically analyzed the cooperative effects and structural deformations of hydrogen-bonded urea, deltamide, and squaramide linear chains using dispersion-corrected density functional theory at BLYP-D3(BJ)/TZ2P level of theory. Our purpose is twofold: (i) reveal the bonding mechanism of the studied systems that lead to their self-assembly in linear chains; and (ii) rationalize the C-C bond equalization in the ring moieties of deltamide and squaramide upon polymerization. Our energy decomposition and Kohn-Sham molecular orbital analyses reveal cooperativity in all studied systems, stemming from the charge separation within the σ-electronic system by charge transfer from the carbonyl oxygen lone pair donor orbital of one monomer towards the σ* N-H antibonding acceptor orbital of the neighboring monomer. This key orbital interaction causes the C=O bonds to elongate, which, in turn, results in the contraction of the adjacent C-C single bonds that, ultimately, makes the ring moieties of deltamide and squaramide to become more regular. Notably, the π-electron delocalization plays a much smaller role in the total interaction between the monomers in the chain.
Authors 6
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Affiliation as printed
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
These authors contributed equally to this work
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University of Perugia · Vrije Universiteit Amsterdam
Affiliation as printed
Department of Chemistry, Biology and Biotechnology University of Perugia Via Elce di Sotto 8 I-06123 Perugia Italy
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Department of Chemistry, Biology and Biotechnology, University of Perugia, Via Elce di Sotto 8, I-06123 Perugia, Italy
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
These authors contributed equally to this work
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Affiliation as printed
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
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Affiliation as printed
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
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University of Perugia · Istituto di Scienze e Tecnologie Chimiche "Giulio Natta"
Affiliation as printed
Department of Chemistry, Biology and Biotechnology University of Perugia Via Elce di Sotto 8 I-06123 Perugia Italy
Istituto di Scienze e Tecnologie Chimiche “Giulio Natta” (CNR-SCITEC) Via Elce di Sotto 8 06123 Perugia Italy
Department of Chemistry, Biology and Biotechnology, University of Perugia, Via Elce di Sotto 8, I-06123 Perugia, Italy
Istituto di Scienze e Tecnologie Chimiche "Giulio Natta" (CNR-SCITEC), Via Elce di Sotto 8, 06123 Perugia, Italy
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Célia Fonseca Guerra corresponding Aachen Leiden Institute of Chemistry Leiden Institute of Chemistry, Gorlaeus Laboratories
Leiden University · Vrije Universiteit Amsterdam
Affiliation as printed
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
Leiden Institute of Chemistry, Gorlaeus Laboratories Leiden University Einsteinweg 55 2333 CC Leiden The Netherlands
Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands
Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands
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