Simultaneous and in situ syntheses of an enantiomeric pair of homochiral polymers as their perfect stereocomplex in a crystal

Worch, J. C. et al. Stereochemical enhancement of polymer properties. Nat. Rev. Chem. 3, 514–535 (2019).Article 
CAS 

Google Scholar 
Popowski, Y., Lu, Y., Coates, G. W. & Tolman, W. B. Stereocomplexation of stereoregular aliphatic polyesters: Change from amorphous to semicrystalline polymers with single stereocenter inversion. J. Am. Chem. Soc. 144, 8362–8370 (2022).Article 
CAS 
PubMed 

Google Scholar 
Zhu, J.-B. & Chen, E. Y.-X. Catalyst-sidearm-induced stereoselectivity switching in polymerization of a racemic lactone for stereocomplexed crystalline polymer with a circular life cycle. Angew. Chem. Int. Ed. 58, 1178–1182 (2019).Article 
CAS 

Google Scholar 
Zhu, J.-B., Watson, E. M., Tang, J. & Chen, E. Y.-X. A synthetic polymer system with repeatable chemical recyclability. Science 360, 398–403 (2018).Article 
ADS 
CAS 
PubMed 

Google Scholar 
Longo, J. M., DiCiccio, A. M. & Coates, G. W. Poly(propylene succinate): a new polymer stereocomplex. J. Am. Chem. Soc. 136, 15897–15900 (2014).Article 
CAS 
PubMed 

Google Scholar 
Liu, Y., Ren, W.-M., Wang, M., Liu, C. & Lu, X.-B. Crystalline stereocomplexed polycarbonates: Hydrogen-bond-driven interlocked orderly assembly of the opposite enantiomers. Angew. Chem. Int. Ed. 54, 2241–2244 (2015).Article 
CAS 

Google Scholar 
Vidal, F., Falivene, L., Caporaso, L., Cavallo, L. & Chen, E. Y.-X. Robust cross-linked stereocomplexes and c60 inclusion complexes of vinyl-functionalized stereoregular polymers derived from chemo/stereoselective coordination polymerization. J. Am. Chem. Soc. 138, 9533–9547 (2016).Article 
CAS 
PubMed 

Google Scholar 
Nagy-Smith, K. et al. Molecular, local, and network-level basis for the enhanced stiffness of hydrogel networks formed from coassembled racemic peptides: predictions from pauling and corey. ACS Cent. Sci. 3, 586–597 (2017).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Tu, Y.-M. et al. Biobased high-performance aromatic–aliphatic polyesters with complete recyclability. J. Am. Chem. Soc. 143, 20591–20597 (2021).Article 
CAS 
PubMed 

Google Scholar 
Marin, P. et al. Polymerization of rac-lactide using achiral iron complexes: access to thermally stable stereocomplexes. Angew. Chem. Int. Ed. 58, 12585–12589 (2019).Article 
ADS 
CAS 

Google Scholar 
McGuire, T. M. et al. Control of crystallinity and stereocomplexation of synthetic carbohydrate polymers from d- and l-xylose. Angew. Chem. Int. Ed. 60, 4524–4528 (2021).Article 
CAS 

Google Scholar 
Andersson, S. R., Hakkarainen, M., Inkinen, S., Södergård, A. & Albertsson, A.-C. Polylactide stereocomplexation leads to higher hydrolytic stability but more acidic hydrolysis product pattern. Biomacromolecules 11, 1067–1073 (2010).Article 
CAS 
PubMed 

Google Scholar 
Abdilla, A. et al. Polymer stereocomplexation as a scalable platform for nanoparticle assembly. J. Am. Chem. Soc. 142, 1667–1672 (2020).Article 
CAS 
PubMed 

Google Scholar 
Sun, L. et al. Structural reorganization of cylindrical nanoparticles triggered by polylactide stereocomplexation. Nat. Commun. 5, 5746 (2014).Article 
ADS 
CAS 
PubMed 

Google Scholar 
Kumaki, J., Kawauchi, T., Ute, K., Kitayama, T. & Yashima, E. Molecular weight recognition in the multiple-stranded helix of a synthetic polymer without specific monomer–monomer interaction. J. Am. Chem. Soc. 130, 6373–6380 (2008).Article 
CAS 
PubMed 

Google Scholar 
Kawauchi, T., Kitaura, A., Kumaki, J., Kusanagi, H. & Yashima, E. Helix-sense-controlled synthesis of optically active poly(methyl methacrylate) stereocomplexes. J. Am. Chem. Soc. 130, 11889–11891 (2008).Article 
CAS 
PubMed 

Google Scholar 
Ren, J. M. et al. DNA-inspired strand-exchange for switchable pmma-based supramolecular morphologies. J. Am. Chem. Soc. 141, 2630–2635 (2019).Article 
CAS 
PubMed 

Google Scholar 
Wu, X. et al. Thermally stable, biocompatible, and flexible organic field-effect transistors and their application in temperature sensing arrays for artificial skin. Adv. Funct. Mater. 25, 2138–2146 (2015).Article 
CAS 

Google Scholar 
Li, Y. et al. Broad-spectrum antimicrobial and biofilm-disrupting hydrogels: Stereocomplex-driven supramolecular assemblies. Angew. Chem. Int. Ed. 52, 674–678 (2013).Article 
CAS 

Google Scholar 
Michell, R. M. & Ladelta, V. Da Silva, E., Müller, A. J. & Hadjichristidis, N. Poly(lactic acid) stereocomplexes based molecular architectures: Synthesis and crystallization. Prog. Polym. Sci. 146, 101742 (2023).Article 
CAS 

Google Scholar 
Guo, M. et al. Recent advances in enhancing stereocomplexation between poly(lactide) enantiomeric chains. Phys. Chem. Chem. Phys. 25, 17737–17758 (2023).Article 
CAS 
PubMed 

Google Scholar 
Pan, P. et al. Competitive stereocomplexation, homocrystallization, and polymorphic crystalline transition in poly(l-lactic acid)/poly(d-lactic acid) racemic blends: Molecular weight effects. J. Phys. Chem. B. 119, 6462–6470 (2015).Article 
CAS 
PubMed 

Google Scholar 
Pan, P. et al. Stereocomplexation of high-molecular-weight enantiomeric poly(lactic acid)s enhanced by miscible polymer blending with hydrogen bond interactions. Polymer 98, 80–87 (2016).Article 
CAS 

Google Scholar 
Wan, Z.-Q. et al. Comprehensive understanding of polyester stereocomplexation. J. Am. Chem. Soc. 141, 14780–14787 (2019).Article 
CAS 
PubMed 

Google Scholar 
Ren, J. M. et al. Controlled formation and binding selectivity of discrete oligo(methyl methacrylate) stereocomplexes. J. Am. Chem. Soc. 140, 1945–1951 (2018).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Liu, Y., Fang, L.-M., Ren, B.-H. & Lu, X.-B. Asymmetric alternating copolymerization of CO2 with meso-epoxides: Ring size effects of epoxides on reactivity, enantioselectivity, crystallization, and degradation. Macromolecules 53, 2912–2918 (2020).Article 
ADS 
CAS 

Google Scholar 
Fan, H.-Z. et al. Advancing the development of recyclable aromatic polyesters by functionalization and stereocomplexation. Angew. Chem. Int. Ed 61, e202117639 (2022).Article 
ADS 
CAS 

Google Scholar 
Liu, Y., Wang, M., Ren, W.-M., Xu, Y.-C. & Lu, X.-B. Crystalline hetero-stereocomplexed polycarbonates produced from amorphous opposite enantiomers having different chemical structures. Angew. Chem. Int. Ed. 54, 7042–7046 (2015).Article 
CAS 

Google Scholar 
Auriemma, F. et al. Stereocomplexed poly(limonene carbonate): a unique example of the cocrystallization of amorphous enantiomeric polymers. Angew. Chem. Int. Ed. 54, 1215–1218 (2015).Article 
CAS 

Google Scholar 
Radano, C. P., Baker, G. L. & Smith, M. R. Stereoselective polymerization of a racemic monomer with a racemic catalyst: Direct preparation of the polylactic acid stereocomplex from racemic lactide. J. Am. Chem. Soc. 122, 1552–1553 (2000).Article 
CAS 

Google Scholar 
Zhang, Z., Shi, C., Scoti, M., Tang, X. & Chen, E. Y.-X. Alternating isotactic polyhydroxyalkanoates via site- and stereoselective polymerization of unsymmetrical diolides. J. Am. Chem. Soc. 144, 20016–20024 (2022).Article 
CAS 
PubMed 

Google Scholar 
Widger, P. C. B. et al. Isospecific polymerization of racemic epoxides: a catalyst system for the synthesis of highly isotactic polyethers. Chem. Commun. 46, 2935–2937 (2010).Article 
CAS 

Google Scholar 
Tang, X., Westlie, A. H., Watson, E. M. & Chen, E. Y.-X. Stereosequenced crystalline polyhydroxyalkanoates from diastereomeric monomer mixtures. Science 366, 754–758 (2019).Article 
ADS 
CAS 
PubMed 

Google Scholar 
MacGillivray, L. R. et al. Supramolecular control of reactivity in the solid state: from templates to ladderanes to metal−organic frameworks. Acc. Chem. Res. 41, 280–291 (2008).Article 
CAS 
PubMed 

Google Scholar 
Hema, K. & Sureshan, K. M. Topochemical azide–alkyne cycloaddition reaction. Acc. Chem. Res. 52, 3149–3163 (2019).Article 
CAS 
PubMed 

Google Scholar 
Sun, A., Lauher, J. W. & Goroff, N. S. Preparation of poly(diiododiacetylene), an ordered conjugated polymer of carbon and iodine. Science 312, 1030–1034 (2006).Article 
ADS 
CAS 
PubMed 

Google Scholar 
Hema, K. et al. Topochemical polymerizations for the solid-state synthesis of organic polymers. Chem. Soc. Rev. 50, 4062–4099 (2021).Article 
CAS 
PubMed 

Google Scholar 
Khazeber, R. & Sureshan, K. M. Topochemical ene–azide cycloaddition reaction. Angew. Chem. Int. Ed. 60, 24875–24881 (2021).Article 
CAS 

Google Scholar 
Khazeber, R. & Sureshan, K. M. Single-crystal-to-single-crystal translation of a helical supramolecular polymer to a helical covalent polymer. Proc. Natl. Acad. Sci. USA. 119, e2205320119 (2022).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Khazeber, R., Kana, G. S. & Sureshan, K. M. Massive molecular motion in crystal leads to an unexpected helical covalent polymer in a solid-state polymerization. Angew. Chem. Int. Ed 63, e202316513 (2024).Article 
CAS 

Google Scholar 
Raju, C., Kunnikuruvan, S. & Sureshan, K. M. Topochemical cycloaddition reaction between an azide and an internal alkyne. Angew. Chem. Int. Ed 61, e202210453 (2022).Article 
CAS 

Google Scholar 
Ravi, A., Shijad, A. & Sureshan, K. M. Single-crystal-to-single-crystal synthesis of a pseudostarch via topochemical azide–alkyne cycloaddition polymerization. Chem. Sci. 12, 11652–11658 (2021).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Madhusudhanan, M. C., Balan, H., Werz, D. B. & Sureshan, K. M. Azide⋅⋅⋅oxygen interaction: A crystal engineering tool for conformational locking. Angew. Chem. Int. Ed. 60, 22797–22803 (2021).Article 
CAS 

Google Scholar 
Hu, Y. et al. Single crystals of mechanically entwined helical covalent polymers. Nat. Chem. 13, 660–665 (2021).Article 
CAS 
PubMed 

Google Scholar 
Guo, Q.-H. et al. Single-crystal polycationic polymers obtained by single-crystal-to-single-crystal photopolymerization. J. Am. Chem. Soc. 142, 6180–6187 (2020).Article 
PubMed 

Google Scholar 
Khazeber, R., Pathak, S. & Sureshan, K. M. Simultaneous and in situ syntheses of an enantiomeric pair of homochiral polymers as their perfect stereocomplex in a crystal. figshare. Dataset. https://doi.org/10.6084/m9.figshare.26302075 (2024).