This paper reports the first examples of poly(diaminosulfide)s that were synthesized by the reaction of a sulfur transfer reagent and several secondary diamines. The diaminosulfide group has the general structure of R2N-S-NR2 and, although it has been used in the synthesis of small molecules, it has never been utilized in the synthesis of macromolecules until this report. A series of poly(diaminosulfide)s were synthesized at elevated temperatures, and the molecular weights of the polymers were as high as 12,400 g mol−1 with conversions for the polymerization reaction up to 99%. The rate constants for the transamination reactions that lead to the polymers were measured in several solvents to provide an understanding the reaction conditions necessary to polymerize the monomers. The degradation of diaminosulfides were studied in D2O, C6D6, CD3OD, CDCl3, and DMSO-d6/D2O to demonstrate that they were very stable in organic solvents but degraded within hours under aqueous conditions. These results clearly demonstrated that diaminosulfides are very stable in organic solvents under ambient conditions. Poly(diaminosulfide)s have sufficient stabilities to be useful for many applications. The ability of these polymers to function as drug delivery vehicles were studied by the fabrication of nanoparticles of a water-insoluble poly(diaminosulfide) with a dye. The microparticles were readily absorbed into human embryonic 293 cells and possessed no measureable toxicity towards these same cells.

The synthesis and some of the physical properties of the first poly(disulfidediamines) are reported. The disulfidediamine functional group (R2NSSNR2) possesses a disulfide bond in a unique environment that leads to a low bond dissociation energy (calculated BDE of 43.1 kcal mol–1). These polymers were synthesized in high yields and with conversions up to >98% by reactions between secondary diamines and a new disulfide monomer. The disulfide monomer was synthesized in two steps without the need for column chromatography. The polymerizations were robust and completed at room temperature, under ambient atmospheric conditions, and in solvents that were used as purchased. These polymers were stable, but they rapidly decomposed under acidic, aqueous conditions or by heating to 175 °C as shown by thermal gravimetric analysis. The first fully conjugated poly(disulfidediamine) was synthesized, and its electrical conductivity was characterized in the solid state.

A new method for detecting polymerization and amplifying initiator signals is established by fluorogenic atom transfer radical polymerization.

The turnovers of a gold(III) chloride catalyst were increased by 3,300% with the addition of several equivalents of 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) and catalytic amounts of copper(II) chloride. A three‐component coupling reaction between piperidine, phenylacetylene, and benzaldehyde yielded a propargylic amine in quantitative conversions and isolated yields when gold(III) chloride was added in catalytic amounts, but the gold catalyst decomposed and had little to no reactivity when a second set of piperidine, phenylacetylene, and benzaldehyde was added after the reaction was complete. Thus, only one cycle was possible with gold(III) chloride. The addition of TEMPO and copper(II) chloride to reactions with gold(III) chloride maintained the catalytic activity of gold for up to 33 cycles. This result demonstrates a new way to greatly increase the turnovers of a gold(III) chloride catalyst with the addition of inexpensive, commercially available reagents.