Detailed Approach to Investigate Thermodynamically Controlled Supramolecular Copolymerizations

Lafayette N J de Windt; Chidambar Kulkarni; Huub M M Ten Eikelder; Albert J Markvoort; E W Meijer; Anja R A Palmans

doi:10.1021/acs.macromol.9b01502

Detailed Approach to Investigate Thermodynamically Controlled Supramolecular Copolymerizations

Macromolecules. 2019 Oct 8;52(19):7430-7438. doi: 10.1021/acs.macromol.9b01502. Epub 2019 Sep 26.

Authors

Lafayette N J de Windt¹, Chidambar Kulkarni¹, Huub M M Ten Eikelder¹, Albert J Markvoort¹, E W Meijer¹, Anja R A Palmans¹

Affiliation

¹ Institute for Complex Molecular Systems, Laboratory of Macromolecular and Organic Chemistry, and Computational Biology Group, Eindhoven University of Technology, P. O. Box 513, 5600 MB Eindhoven, The Netherlands.

Abstract

Elucidating the microstructure of supramolecular copolymers remains challenging, despite the progress in the field of supramolecular polymers. In this work, we present a detailed approach to investigate supramolecular copolymerizations under thermodynamic control. Our approach provides insight into the interactions of different types of monomers and hereby allows elucidating the microstructure of copolymers. We select two monomers that undergo cooperative supramolecular polymerization by way of threefold intermolecular hydrogen bonding in a helical manner, namely, benzene-1,3,5-tricarboxamide (BTA) and benzene-1,3,5-tris(carbothioamide) (thioBTA). Two enantiomeric forms and an achiral analogue of BTA and thioBTA are synthesized and their homo- and copolymerizations are studied using light scattering techniques, infrared, ultraviolet, and circular dichroism spectroscopy. After quantifying the thermodynamic parameters describing the homopolymerizations, we outline a method to follow the self-assembly of thioBTA derivatives in the copolymerization with BTA, which involves monitoring a characteristic spectroscopic signature as a function of temperature and relative concentration. Using modified types of sergeants-and-soldiers and majority-rules experiments, we obtain insights into the degree of aggregation and the net helicity. In addition, we apply a theoretical model of supramolecular copolymerization to substantiate the experimental results. We find that the model describes the two-component system well and allows deriving the hetero-interaction energies. The interactions between the same kinds of monomers (BTA-BTA and thioBTA-thioBTA) are slightly more favorable than those between different monomers (BTA-thioBTA), corresponding to a nearly random copolymerization. Finally, to study the interactions of the monomers at the molecular level, we perform density functional theory-based computations. The results corroborate that the two-component system exhibits a random distribution of the two monomer units along the copolymer chain.