A new, simple, and effective method for the diazotization of a wide range of arylamines has been developed by using a polymer-supported diazotization agent in the presence of p-toluenesulfonic acid. Various pure arenediazonium tosylates with unusual stabilities can be easily prepared by this method. As a result, these salts are useful and versatile substrates for subsequent transformations, such as halogenation and Heck-type reactions. The unusual stabilities of arenediazonium tosylates are also preliminarily discussed with their X-ray structures.

The first method of plasmon-induced nitroxide-mediated polymerization on periodical gold gratings has been developed.

The optimization of a palladium-catalyzed Heck−Matsuda reaction using an optimization algorithm is presented. We modified and implemented the Nelder−Mead method in order to perform constrained optimizations in a multidimensional space. We illustrated the power of our modified algorithm through the optimization of a multivariable reaction involving the arylation of a deactivated olefin with an arenediazonium salt. The great flexibility of our optimization method allows to fine-tune experimental conditions according to three different objective functions: maximum yield, highest throughput, and lowest production cost. The beneficial properties of flow reactors associated with the power of intelligent algorithms for the fine-tuning of experimental parameters allowed the reaction to proceed in astonishingly simple conditions unable to promote the coupling through traditional batch chemistry.

Thermally stable organic diradicals with at riplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications.A series of phenylene-bridged diradicals with oxoverdazyla nd nitronyl nitroxide units were synthesized via ap alladiumcatalyzedc ross-coupling reaction of iodoverdazyls with an itronyl nitroxide-2-ide gold(I) complex with high yields.T he diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180 8 8C. Fort he diradicals,b oth substantial AF (DE ST %À64 cm À1)a nd FM (DE ST ! 25 and 100 cm À1)intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para-or meta-phenylene) and by the type of oxoverdazylb lock(C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique onedimensional exchange-coupled chains with strong intra-and weak inter-diradical ferromagnetic coupling.

Thermally resistant air-stable organic triradicals with a quartet ground state and a large energy gap between spin states are still unique compounds. Moreover, stable triradicals with bridging units of the ethylene-1,1-diyl type and ferromagnetic coupling are limited to the family of nitroxides. In this work, for the first time, we designed and prepared the triradical having a quartet ground state based on oxoverdazyl and nitronyl nitroxide radical fragments. The triradical and appropriate triplet diradical precursor were synthesized via a palladium-catalyzed cross-coupling reaction of diiodoverdazyl with nitronyl nitroxide-2-ide gold(I) complex. Both the di-and triradical are air-stable and possess good thermal stability with decomposition onset at ∼160 °C in an inert atmosphere. X-ray diffraction analysis of single crystals confirmed the presence of verdazyl and nitroxide radical centers. In the diradical, the verdazyl and nitronyl nitroxide centers showed fully reversible redox waves. In case of the triradical, the electrochemical processes occur practically at the same redox potentials but become quasi-reversible for the nitroxide moieties. Magnetic properties of the di-and triradical were characterized by a SQUID magnetometry of polycrystalline powders and by EPR spectroscopy in different matrices. Collected data analyzed using of the highlevel quantum chemical calculations confirmed that the di-and triradical have high-spin ground states. Unique high stability of prepared verdazyl-nitronylnitroxyl triradical opens new perspectives for further functionalization and design of high-spin systems with four or more spins.

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A general and effective method for the synthesis of 3‐phenylveradzyl radicals bearing a variety of iodophenyl substituents has been developed. The synthesized radicals have been characterized by ESR, UV/Vis spectroscopy, and cyclic voltammetry. Structures of biphenyl‐substituted radicals have been solved by X‐ray crystal structure analysis. The synthesized iodoverdazyls are applicable in the Sonogashira coupling reaction for the preparation of a wide range of ethynyl derivatives. Both N‐2 and C‐6 substituents were functionalized through Sonogashira coupling.