Through the simultaneous use of three orthogonal dynamic covalent reactions, namely disulfide, boronate, and acyl hydrazone formation, we conceived a facile and versatile protocol to spatially organize tailored chromophores, which absorb in the blue, red, and yellow regions, on a preprogrammed α-helix peptide. This approach allowed the assembly of the dyes in the desired ratio and spacing, as dictated by both the relative positioning and distribution of the recognition units on the peptide scaffold. Steady-state UV/Vis absorption and emission studies suggest an energy transfer from the yellow and red donors to the blue acceptor. A molecular dynamics simulation supports the experimental findings that the helical structure is maintained after the assembly and the three dyes are confined in defined conformational spaces.

Photo-release of triphenylphosphine from a sulfonamide azobenzene ruthenium-arene complex was exploited to activate Pd II Cl 2 into Pd 0 catalyst, for the photo-initiation of Sonogashira cross-coupling. The transformation was initiated on demand -by using simple white LED strip lights -with a high temporal response and the ability to control reaction rate by changing the irradiation time. Various substrates were successfully applied to this photo-initiated cross-coupling, thus illustrating the wide functional-group tolerance of our photo-caged catalyst activator, without any need for sophisticated photochemistry apparatus.

AzaBenzannulated perylenediimide (AzaBPDI) dyes were synthesized in high yields via a new reaction sequence involving an imine condensation followed by visible light-induced photocyclization. The large scope and efficiency of this alternative to the Pictet–Spengler reaction are demonstrated, allowing easy preparation of dimeric AzaBPDI as potential non-fullerene acceptors for organic solar cells.

Mimicking nature to develop light-harvesting materials is a timely challenge. This tutorial review examines the chemical strategies to engineer and customise innovative multi-coloured architectures with specific light-absorbing and emitting properties.

Perylenediimide (PDI) is one of the most important classes of dyes and is intensively explored in the field of functional organic materials. The functionalization of this electron-deficient aromatic core is well-known to tune the outstanding optoelectronic properties of PDI derivatives. In this respect, the functionalization has been mostly addressed in bay-positions to halogenated derivatives through nucleophilic substitutions or metal-catalyzed coupling reactions. Being aware of the synthetic difficulties of obtaining the key intermediate 1-bromoPDI, we will present as an alternative in this review the potential of 1-nitroPDI: a powerful building block to access a large variety of PDI-based materials.

Palladium-catalyzed cross-coupling reactions are nowadays essential in organic synthesis for the construction of C–C, C–N, C–O, and other C-heteroatom bonds. The 2010 Nobel Prize in Chemistry to Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki was awarded for the discovery of these reactions. These great advances for organic chemists stimulated intense research efforts worldwide dedicated to studying these reactions. Among them, the Suzuki–Miyaura coupling (SMC) reaction, which usually involves an organoboron reagent and an organic halide or triflate in the presence of a base and a palladium catalyst, has become, in the last few decades, one of the most popular tools for the creation of C–C bonds. In this review, we present recent progress concerning the SMC reaction with the original use of nitroarenes as electrophilic coupling partners reacting with the organoboron reagent.

A series of perylenediimide (PDI)-based multimers were synthesized using an original Suzuki-Miyaura Coupling (SMC) reaction. The new approach considers the reaction between 1-nitroPDI as the electrophilic reagent with a wide variety of boronic esters to reach PDI dimers, trimers and tetramers which are of particular interest as Non-Fullerene Acceptors (NFAs) in organic photovoltaics. In this work, we compared the reactivity of 1-bromoPDI and 1-nitroPDI towards this palladocatalyzed cross-coupling reaction. Considering that 1-nitroPDI is more accessible in terms of selectivity, time reaction, purification efficiency, atom economy, etc, we have shown that the use of nitroarenes is largely favored in the preparation of these PDI- [a] 7635 Scheme 2. Experimental conditions used for the multimerization by SMC using 1-bromoPDI or 1-nitroPDI as electrophilic reagent. Here the example for the dimerization is given. 7639 Figure 9. Frontier Molecular Orbitals of functionalized PDI building blocks 2, 3, 7, 9 and 10 measured by cyclic voltammetry (CV) (solid line) and optical properties (dotted line).

This review summarizes the most noteworthy achievements in the field of C–O and C–N bond formation by hydroalkoxylation and hydroamination reactions on unactivated alkenes (including 1,2- and 1,3-dienes) promoted by earth-abundant 3d transition metal catalysts based on manganese, iron, cobalt, nickel, copper and zinc. The relevant literature from 2012 until early 2021 has been covered.