Modern Synthetic Tools Toward the Preparation of Sophisticated Phthalocyanine‐Based Photoactive Systems

Abstract

Phthalocyanines are ideal components in a variety of electronic applications due to their extraordinary photophysical characteristics combined with their synthetic versatility and robustness. They have attracted substantial attention in recent decades and are now established building blocks of sophisticated molecular materials. Synthetically, a great deal of this progress is attributed to the use of modern synthetic tools, which gave rise to phthalocyanine-based systems that could not have been envisaged in the past. In particular, Pd-catalyzed cross-coupling reactions, together with other transition-metal-catalyzed procedures, "click" chemistry, and ruthenium metathesis have been employed extensively en route to an abundant range of elaborate phthalocyanine mono- and multicomponent photoactive architectures. Herein, we describe the synthesis of a selection of key examples that are representative in certain optoelectronic applications.

Distance Matters: Effect of the Spacer Length on the Photophysical Properties of Multimodular Perylenediimide–Silicon Phthalocyanine–Fullerene Triads

“…There are a variety of chemically stable building blocks, easy to synthesize and functionalize and, therefore, with tunable light harvesting and photophysical properties, suitable to “construct” high‐performance artificial photosynthetic systems. Among the available building blocks, perylenediimides (PDI), phthalocyanines (Pcs) and C 60 ‐fullerene stand up. PDI and Pcs exhibit large molar extinction coefficients, up to 10 5 m −1 cm −1 , with absorption and emission spectra covering the 400–800 nm region.…”

“…[9,10] There are av ariety of chemically stable building blocks, easy to synthesize and functionalize and, therefore, with tunable light harvesting and photophysical properties, suitable to "construct" high-performance artificial photosynthetic systems. Among the availableb uilding blocks, perylenediimides (PDI), [11][12][13] phthalocyanines (Pcs) [14][15][16] and C 60 -fullerene [17,18] stand up. PDI and Pcs exhibit large molare xtinction coefficients, up to 10 5 m À1 cm À1 ,w ith absorption and emission spectra covering the 400-800nmr egion.T hey also present genuine electron-acceptora nd electron-donor characters, respectively,w hich can be modulated through chemicalm odifications.O nt he other hand, C 60 -fullerene is aw ell-known electron-acceptorm oiety,d ue to its large p-electron 3D spherical system, which makes it to presentasmall reorganization energya fter reduction, which resultsi nf ast charges eparation process and slow recombination of the formed charged separated state.…”

A hindered subphthalocyanine that forms crystals with included aromatic solvent but will not play ball with C60

“…In addition to providing exceptional stability, the structure of the PNCs provides intimate contact between of one of the most studied photoelectron donors (phthalocyanine) with the most studied class of photoelectron acceptor (fullerene). 83,84 The combination of these highly functional components within a porous material suggests applications in light-harvesting, photovoltaics and photocatalysis, for which the stability demonstrated in this study will be beneficial. 85 7 Here, we describe the stability of a fullerene stabilised phthalocyanine based porous molecular material to high-vacuum, and describe changes in the structure of this material when exposed to O2 and CO whilst simultaneously conducting insitu X-ray diffraction experiments on EH2 on station I19 at the Diamond Light Source using an in-situ gas cell, the design of which has been previously discussed ( §2.2).…”

“…80 PSM in the MOF community is a field in its own right, and has been the subject of numerous reviews. [81][82][83] PSM allows the synthesis of MOFs which are impossible to make via direct synthetic approaches, opening up new avenues of chemistry and potential applications for MOFs. McKellar et al went on to investigate STAM-1 at high-pressure with various PTMs including methanol, ethanol, acetonitrile, and acetaldehyde.…”

Human serum albumin nanoparticles loaded with phthalocyanine dyes for potential use in photodynamic therapy for atherosclerotic plaques

“…[25][26][27][28][29] For example, silicon-based phthalocyanine (Pc4) is a known secondgeneration photosensitizer, generating singlet oxygen upon photoirradiation with an absorption in the far red at 675 nm and has been used for treating cancer and other diseases. [30][31][32][33][34] Given the additional fluorescence properties of photosensitizers, they can be used both as therapeutics and as diagnostics, sometimes called "theranostics." One of the drawbacks is that the hydrophobic sensitizer mainly accumulates in the cell membrane therefore killing the cell by necrosis rather than by apoptosis.…”