Facile Synthesis of\nFunctional Polytrithiocarbonates\nfrom Multicomponent Tandem Polymerizations of CS<sub>2</sub>, Thiols,\nand Alkyl Halides

Polytrithiocarbonates have attracted significant attention\nrecently\nbecause of their good thermal stability, light refractivity, crystallinity,\nand mechanical properties; however, the exploration of their structures\nand functionalities has been limited by their synthetic approaches.\nMulticomponent polymerization featuring simple monomers, mild conditions,\ndiversified product structures, and high efficiency could provide\na powerful and versatile tool to synthesize various polytrithiocarbonates\nfrom commercially available monomers. Herein, a robust and efficient\nmulticomponent tandem polymerization (MCTP) of CS<sub>2</sub>, dithiols,\nand alkyl halides was developed in DMF with K<sub>2</sub>CO<sub>3</sub> at room temperature in air to synthesize 12 polytrithiocarbonates\nwith diversified and systematically tuned structures, high molecular\nweights (<i>M</i><sub>n</sub>s up to 37900 g/mol), and high\nyields (up to 93%). Depending on the different polymer backbone structures,\namorphous polytrithiocarbonates showed excellent breaking elongations,\nand crystallinic polytrithiocarbonates possessed a large process temperature\nwindow (about 200 °C) and good mechanical performance (σ<sub>B</sub> of 23.6 MPa and <i>ε</i><sub>B</sub> of 858%),\nwhose tensile strength could be dramatically enhanced to 87.5 MPa\nafter uniaxial extension deformation. The upper critical solution\ntemperature (UCST) in organic solvents, together with nonconventional\nluminescence, were observed for the crystallinic polytrithiocarbonates,\neven without any aromatic ring. This efficient, robust, mild, and\neconomic MCTP of CS<sub>2</sub> thus opened up an avenue for the facile\nconstruction of polytrithiocarbonates with structural diversity, bringing\nmodulable mechanical, thermal, luminescent, and thermal-responsive\nproperties, which would greatly broaden the scope of structures and\napplications of sulfur-containing polymers.