Distinct Pathways in “Thermally Bisignate Supramolecular Polymerization”: Spectroscopic and Computational Studies

Kotagiri, Venkata Rao and Mabesoone, Mathijs F J and Miyajima, Daigo and et al, . (2020) Distinct Pathways in “Thermally Bisignate Supramolecular Polymerization”: Spectroscopic and Computational Studies. Journal of the American Chemical Society. pp. 1-8. ISSN 0002-7863 (In Press)

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Abstract

In general, supramolecular polymers are thermally labile in solution and easily depolymerized upon heating. This dynamic nature is beneficial in many aspects but limits certain applications. Recently, we developed “thermally bisignate supramolecular polymerization”, through which a polymer is formed upon heating as well as cooling in a hydrocarbon solvent containing a small amount of alcohol. Here, we present a detailed mechanistic picture for this polymerization based on both spectroscopic and computational studies. For this particular type of polymerization, we mainly employed a copper porphyrin derivative (<b>^(<i>S</i>)POR_Cu</b>) as a monomer with eight hydrogen-bonding (H-bonding) amide units in its chiral side chains. Because of a strong multivalent interaction, the resulting supramolecular polymer displayed an extraordinarily high thermal stability in a hydrocarbon medium such as methylcyclohexane (MCH)/chloroform (CHCl₃) (98/2 <i>v</i>/<i>v</i>; denoted as MCH*). However, when a small volume (< 2.0 vol%) of ethanol (EtOH) was added to this solution at ambient temperatures as a H-bond scavenger, the supramolecular polymer dissociated into its monomer. Here, it should be noted that, both upon cooling (clustering of EtOH) and heating (lower-critical-solution-temperature behavior, LCST), the monomer was liberated from the H-bond scavenger and underwent supramolecular polymerization. In the present article, we conducted detailed spectroscopic studies, analyzed the results using theoretical models, and eventually succeeded in supporting the pathways explaining why the monomer deactivated by the H-bond scavenger, turns active upon both heating and cooling. We also investigated the thermally bisignate nature of the supramolecular polymerization of other monomers such as triphenylamine (^{(<b><i>S</i>)}TPA</b>) and pyrene (<b>^(<i>S</i>)Py</b>) derivatives together with free-base (<b>^(<i>R</i>)POR_2H</b>) and zinc porphyrin (<b>^(<i>S</i>)POR_Zn</b>) derivatives and rationalized the large potential for this multicomponent supramolecular polymerization.

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IITH Creators:	IITH Creators ORCiD Kotagiri, Venkata Rao https://orcid.org/0000-0002-6821-6241
Item Type:	Article
Additional Information:	This work was financially supported by a JSPS Grant-in-Aid for Scientific Research (S) (18H05260) for T.A. on "Innovative Functional Materials based on Multi-Scale Interfacial Molecular Science" . D.M. is thankful for the financial support of the Grant-in-Aid for Young Scientist A (15H05487) and Coordination Asymmetry (JP17H05394). K.V.R. thanks the RIKEN for the postdoctoral fellowship and IIT Hyderabad for financial support. M.F.J.M. and E.W.M. acknowledge financial support from NWO (TOP-PUNT Grant no. 10018944) and the Dutch Ministry of Education Culture and Science (Gravitation program no. 024.001.035).
Uncontrolled Keywords:	Computational studies; High thermal stability; Lower critical solution temperature behavior; Multivalent interactions; Porphyrin derivatives; Spectroscopic studies; Supramolecular polymerization; Supramolecular polymers
Subjects:	Chemistry
Divisions:	Department of Chemistry
Depositing User:	Team Library
Date Deposited:	13 Dec 2019 10:01
Last Modified:	31 Oct 2022 08:38
URI:	http://raiithold.iith.ac.in/id/eprint/7150
Publisher URL:	http://doi.org/10.1021/jacs.9b12044
OA policy:	https://v2.sherpa.ac.uk/id/publication/7788
Related URLs:	Google Scholar Author

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