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Single-Crystal-to-Single-Crystal Synthesis of a Polymer in Two Distinct Topologies.
Angew Chem Int Ed Engl
January 2025
IITH: Indian Institute of Technology Hyderabad, Chemistry, Kandi, Sangaredddy, 502285, INDIA.
A squaramide-based monomer, designed for topochemical azide-alkyne cycloaddition (TAAC) polymerization, crystallizes as two polymorphs, M1 and M2, both having crystal packing suitable for topochemical polymerization. The hydrogen-bonding between squaramide units bias the molecular organization in both the polymorphs. 3D packing of H-bonded stacks of monomer lead to juxtaposition of azide and alkyne units of adjacent molecules in a transition-state-like arrangement for their regiospecific cycloaddition reaction.
View Article and Find Full Text PDFToward Sustainable Polydienes.
J Am Chem Soc
January 2025
Davidson School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United States.
The sustainable management of polydiene waste represents a formidable challenge in the realm of polymer chemistry, given the extensive industrial utilization of polydienes due to their superior elastomeric properties. This comprehensive Perspective addresses the multifaceted obstacles hindering efficient recycling of polydienes, encompassing environmental concerns, technical limitations, and economic disincentives. We systematically dissect the influence of polydienes' chemical structures on their recyclability, tracing the evolution of polydiene utilization and disposal practices while assessing the current landscape of waste management strategies.
View Article and Find Full Text PDFSupramolecular Preorganization of Amine-functionalized Diacetylene Monomers in their Crystals Allows their Topochemical Polymerization to Polydiacetylenes Capable of CO Capture.
Chemistry
January 2025
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Kerala, 695551, India.
We designed and synthesized three diacetylene monomers M1-M3 having two NH groups. As anticipated, the NH groups aided the preorganization of these monomers by N-H…N hydrogen bonding. In the crystals of monomer M1 and M2, the intermolecular N-H…N hydrogen bonding preorganized the diyne units in an orientation suitable for their topochemical polymerization, but in the case of monomer M3, the distance was slightly larger than that recommended for the topochemical reaction.
View Article and Find Full Text PDFA Malleable Collagen-Mimic that Undergoes Moisture-Induced Hardening for Gluing Hydrophilic Surfaces.
Angew Chem Int Ed Engl
January 2025
School of Chemistry, IISER Thiruvananthapuram, Kerala, 695551, India.
A collagen-inspired helical protein-mimic has been synthesized via topochemical polymerization of a designed tripeptide monomer. In the monomer crystal, molecules arrange in a head-to-tail manner, forming supramolecular helices. The azide and alkyne of adjacent molecules in the supramolecular helix are proximally preorganized in a ready-to-react arrangement.
View Article and Find Full Text PDFEndowing single-crystal polymers with circularly polarized luminescence.
Nat Commun
January 2025
Key Laboratory for Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
The preparation of single-crystal polymers with circularly polarized luminesce (CPL) remains a challenging task in chemistry and materials science. Herein, we present the single-crystal-to-single-crystal topochemical photopolymerization of a chiral organic salt to achieve this goal. The in-situ reaction of 1,4-bis((E)-2-(pyridin-4-yl)vinyl)benzene (1) with chiral (+)- or (-)-camphorsulfonic acid (CSA) gives the monomer crystal 1[( + )/( - )-CSA] showing yellow CPL with a high luminescent dissymmetry factor |g| of 0.
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