Tuning Supramolecular Polymer Assembly through Stereoelectronic Interactions
The supramolecular polymerization of 2,11-dithia[3.3]paracyclophanes through self-complementary intermolecular and transannular amide hydrogen bonding is presented. An n → π* interaction between the amide hydrogen bonding units and the central bridging atom results from the single-point exchange of a carbon atom for a sulfur atom. This orbital donor-acceptor interaction can be strengthened by oxidizing the sulfide to a sulfone which acts to shorten the donor···acceptor distance and increase orbital overlap. Experimental signatures of the increased n → π* interaction include larger isodesmic polymerization elongation constants in solution, changes in characteristic bond stretching frequencies, and geometric/structural changes evaluated by X-ray crystallography. The experimental data are supported by extensive computational investigations of both assembling and nonassembling 2,11-dithia[3.3]paracyclophanes as well as a rationally designed model system to confirm the role of stereoelectronic effects on supramolecular polymer assembly.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:143 |
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| Enthalten in: |
Journal of the American Chemical Society - 143(2021), 32 vom: 18. Aug., Seite 12688-12698 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Henderson, Will R [VerfasserIn] |
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| Links: |
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| Themen: |
Amides |
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| Anmerkungen: |
Date Completed 02.02.2022 Date Revised 02.02.2022 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/jacs.1c05522 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM328911062 |
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| 100 | 1 | |a Henderson, Will R |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Tuning Supramolecular Polymer Assembly through Stereoelectronic Interactions |
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| 500 | |a Date Revised 02.02.2022 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a The supramolecular polymerization of 2,11-dithia[3.3]paracyclophanes through self-complementary intermolecular and transannular amide hydrogen bonding is presented. An n → π* interaction between the amide hydrogen bonding units and the central bridging atom results from the single-point exchange of a carbon atom for a sulfur atom. This orbital donor-acceptor interaction can be strengthened by oxidizing the sulfide to a sulfone which acts to shorten the donor···acceptor distance and increase orbital overlap. Experimental signatures of the increased n → π* interaction include larger isodesmic polymerization elongation constants in solution, changes in characteristic bond stretching frequencies, and geometric/structural changes evaluated by X-ray crystallography. The experimental data are supported by extensive computational investigations of both assembling and nonassembling 2,11-dithia[3.3]paracyclophanes as well as a rationally designed model system to confirm the role of stereoelectronic effects on supramolecular polymer assembly | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, N.I.H., Extramural | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 4 | |a Research Support, U.S. Gov't, Non-P.H.S. | |
| 650 | 7 | |a Amides |2 NLM | |
| 650 | 7 | |a Macromolecular Substances |2 NLM | |
| 650 | 7 | |a Polymers |2 NLM | |
| 700 | 1 | |a Liu, Guancen |e verfasserin |4 aut | |
| 700 | 1 | |a Abboud, Khalil A |e verfasserin |4 aut | |
| 700 | 1 | |a Castellano, Ronald K |e verfasserin |4 aut | |
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