A library of eight sequence-defined model oligomers, whose sequence is based on a (0,1) binary code, is prepared through chemoselective repeating cycles of amidification and copper-assisted alkyne-azide cycloaddition reactions from a non-modified Wang resin. This library is constructed from two AB (A = acid, B = alkyne) building blocks, i.e., 4-pentynoic acid and 2-methyl-4-pentynoic acid acting, respectively, as non-coding (0) and coding (1) monomer, and 1-amino-11-azido-3,6,9-trioxaundecane as complementary CD (C = amine, D = azide) spacer building block. In particular, encoded triads are synthesized by consecutive covalent attachment of five building blocks (i.e., three coding/non-coding monomers and two spacers). In this communication, optimal protocols for the synthesis of the targeted oligomers are reported along with their full characterization by (1) H NMR, MALDI-TOF mass spectrometry, and size-exclusion chromatography. It is found that all possible encoded triads (i.e., eight possibilities) could be synthesized using this approach. Indeed, monodisperse sequence-defined oligomers are prepared and characterized in all cases.

The synthesis of “precision” polymers with finely controlled molecular structures is an important new development in synthetic polymer chemistry. This trend is the logical outcome of the continuing evolution of the field of polymer synthesis. Indeed, during the last few decades, synthetic tools, such as living ionic polymerizations, controlled radical polymerizations, and click chemistry, have revolutionized the synthesis of polymers with controlled architectures such as block, graft, star, brush, hyperbranched or cyclic polymers. These aspects being solved, it is now time for polymer chemists to address more challenging questions such as the design of monodisperse polymers and the control of primary (i.e., comonomer sequences), secondary (i.e., single‐chain folding), and tertiary (i.e., single‐chain compartmentalization) structures. Here, new synthetic tools have to be developed or imported from other disciplines such as organic chemistry and biochemistry. For instance, solid‐phase iterative chemistry, which was initially introduced for the synthesis of oligopeptides and oligonucleotides, is an interesting methodology for preparing monodisperse sequence‐defined polymers. However, such approaches are usually time‐consuming and request demanding coupling/capping/deprotection steps. Yet, interesting protecting‐group‐free methodologies have been described in recent years for simplifying and accelerating these processes. These promising new approaches are briefly listed and explained in this article.

Carbazole structures are of high interest in photopolymerization due to their enhanced light absorption properties in the near-UV or even visible ranges. Therefore, type I photoinitiators combining the carbazole chromophore to the well-established phosphine-oxides were proposed and studied in this article. The aim of this article was to propose type I photoinitiators that can be more reactive than benchmark phosphine oxides, which are among the more reactive type I photoinitiators for a UV or near-UV light emitting diodes (LED) irradiation. Two molecules were synthesized and their UV-visible light absorption properties as well as the quantum yields of photolysis and photopolymerization performances were measured. Remarkably, the associated absorption was enhanced in the 350–410 nm range compared to benchmark phosphine oxides, and one compound was found to be more reactive in photopolymerization than the commercial photoinitiator TPO-L for an irradiation at 395 nm.