Distinct pathways in "thermally bisignate supramolecular polymerization": spectroscopic and computational studies

Kotagiri Venkata Rao; Mathijs F.J. Mabesoone; Daigo Miyajima; Atsuko Nihonyanagi; E.W. Meijer; Takuzo Aida

doi:10.1021/jacs.9b12044

Distinct pathways in "thermally bisignate supramolecular polymerization": spectroscopic and computational studies

Kotagiri Venkata Rao, Mathijs F.J. Mabesoone, Daigo Miyajima (Corresponding author), Atsuko Nihonyanagi, E.W. Meijer (Corresponding author), Takuzo Aida (Corresponding author)

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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 (^(S)POR_Cu) 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 v/v; 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 monomers. 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 this 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 (^(S)TPA) and pyrene (^(S)Py) derivatives together with free-base (^(R)POR_2H) and zinc porphyrin (^(S)POR_Zn) derivatives and rationalized the large potential for this multicomponent supramolecular polymerization.

Original language	English
Pages (from-to)	598-605
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	142
Issue number	1
DOIs	https://doi.org/10.1021/jacs.9b12044
Publication status	Published - 8 Jan 2020

Funding

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).

Funders	Funder number
Ministerie van Onderwijs, Cultuur en Wetenschap
Japan Society for the Promotion of Science	15H05487, 18H05260, JP17H05394
Ministerie van Onderwijs, Cultuur en Wetenschap	024.001.035
Nederlandse Organisatie voor Wetenschappelijk Onderzoek	10018944

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title = "Distinct pathways in {"}thermally bisignate supramolecular polymerization{"}: spectroscopic and computational studies",

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 ((S)PORCu) 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 v/v; 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 monomers. 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 this 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 ((S)TPA) and pyrene ((S)Py) derivatives together with free-base ((R)POR2H) and zinc porphyrin ((S)PORZn) derivatives and rationalized the large potential for this multicomponent supramolecular polymerization.",

author = "Rao, {Kotagiri Venkata} and Mabesoone, {Mathijs F.J.} and Daigo Miyajima and Atsuko Nihonyanagi and E.W. Meijer and Takuzo Aida",

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Distinct pathways in "thermally bisignate supramolecular polymerization": spectroscopic and computational studies. / Rao, Kotagiri Venkata; Mabesoone, Mathijs F.J.; Miyajima, Daigo (Corresponding author) et al.
In: Journal of the American Chemical Society, Vol. 142, No. 1, 08.01.2020, p. 598-605.

Research output: Contribution to journal › Article › Academic › peer-review

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T1 - Distinct pathways in "thermally bisignate supramolecular polymerization"

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AU - Rao, Kotagiri Venkata

AU - Mabesoone, Mathijs F.J.

AU - Miyajima, Daigo

AU - Nihonyanagi, Atsuko

AU - Meijer, E.W.

AU - Aida, Takuzo

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Distinct pathways in "thermally bisignate supramolecular polymerization": spectroscopic and computational studies

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