Sulfur Conversion to Multifunctional Poly(<i>O</i>-thiocarbamate)s through Multicomponent Polymerizations of Sulfur, Diols, and Diisocyanides

Sulfur, which is generated from the waste byproducts in the oil and gas refinery industry, is an abundant, cheap, stable, and readily available source in the world. However, the utilization of excessive amounts of sulfur is mostly limited, and developing novel methods for sulfur conversion is still a global concern. Here, we report a facile one-step conversion from elemental sulfur to functional poly(<i>O</i>-thiocarbamate)s through a multicomponent polymerization of sulfur, diols, and diisocyanides, which possesses a series of advantages such as mild condition (55 °C), short reaction time (1 h), 100% atom economy, and transition-metal free in the catalyst system. Seven poly(<i>O</i>-thiocarbamate)s are constructed with high yields (up to 95%), large molecular weight (up to 53100 of <i>M</i>_w), good solubility in organic solvents, and completely new polymer structures. The poly(<i>O</i>-thiocarbamate)s possess a high refractive index above 1.7 from 600 to 1700 nm by adjusting the sulfur content. By incorporating tetraphenylethene (TPE) moieties into the polymer structure, the poly(<i>O</i>-thiocarbamate)s can also be designed as fluorescent sensors to detect harmful metal cation of Hg²⁺ in a turn-on mode with high sensitivity (LOD = 32 nM) and excellent selectivity (over interference cations of Pb²⁺, Au³⁺, Ag⁺). Different from the previous reports, the exact coordination structure is first identified by single-crystal X-ray diffraction, which is revealed in a tetracoordination fashion (two sulfur and two chloride) using a model coordination compound.