Development of controlled reactions using an element-based design of azaporphyrinoid materials

Abstract

Phthalocyanines (Pcs) and related macrocycles (azaporphyrinoids) are well-known artificial dyes in modern material chemistry. Several strategies for fine-tuning their optical/electrochemical/aromatic properties have been proposed. The diversity of Pcs enables novel functionalities that can assist in innovative approaches to tune and improve the properties of diverse material. Organic synthesis yields a wide array of organic molecules. Herein, the author describes two methods for developing controlled reactions in organic synthesis: controlled reactions to produce novel Pcs and controlled reactions using Pcs. In particular, the author proposes an “element-based” design strategy to obtain unique properties using a simple synthetic procedure. This strategy permits the fine-tuning of optical properties in the near-infrared (NIR) region (700–1000 nm). These innovations should create further opportunities for flexible applications of NIR light

Applications of red light photoredox catalysis in organic synthesis

“…Recently, with the increasing interest in red light-induced reactions, more applications of porphyrinoids in this field are disclosed. [32][33][34][35][36]40 In 2021, the Furuyama group demonstrated that Ru phthalocyanine (RuPc) 5e could also act as a competent PC (Scheme 5d). 32 Under the red light, the treatment of alkenes 33 with trifluoromethanesulfonyl chloride 60 in the presence of 5e and K 2 HPO 4 furnished trifluoromethylethyl chlorides 61 in 44-91% yields.…”

Controlling the reactivity of phthalonitriles for the efficient synthesis of chiral phthalocyanines with self-assembly abilities

“…[27][28][29][30][31] However, controlling the reactivity of the phthalonitriles on the basis of the different electronic characteristics of the substituents that can modify the involved electrophilicity/nucleophilicity is underdeveloped. 32 One of the outstanding strategies to prepare Pcs with certain chemo-and regiocontrol is the use of bisphthalonitriles linked by constrained binding groups. [16][17][18][19][20] In particular, the introduction of optically active binaphthyl units as bridges deserves special mention since they lead to optically active Pcs thanks to the intrinsic atropisomerism of the binaphthol subunit.…”

Red-Light-Driven Bifunctionalization of Styrene Derivatives

“…5,6 In these systems, the controlled photoexcited state of phthalocyanines is realized through precise modifications of the phthalocyanine structure. 7 Their high rigidity and large molar absorption coefficient are anticipated to enable long-duration operation with a minimal catalyst loading. Thus, longer-wavelength-light-mediated re- actions facilitated by phthalocyanine catalysts can be expected to unveil novel synthetic pathways, particularly the direct modification of visible-light-absorbing materials, tandem reactions with shorter-wavelength-light-mediated reactions, 8 and under shielded conditions such as those in cell reactions.…”

“…Red-to-near-infrared light (600–900 nm), which encompasses a substantial proportion of solar energy, holds promise for selective reactions of diverse substrates and environments due to the limited number of interacting substances in this wavelength region. Nevertheless, the development of catalysts tailored for the appropriate use of this lower-energy light poses considerable challenges and constitutes a nascent area of research in the field of organic synthesis. , A notable contribution from our group in this context was the pioneering development of reactions catalyzed by red-to-near-infrared-activatable phthalocyanine catalysts. , In these systems, the controlled photoexcited state of phthalocyanines is realized through precise modifications of the phthalocyanine structure . Their high rigidity and large molar absorption coefficient are anticipated to enable long-duration operation with a minimal catalyst loading.…”