Complementary Syntheses Giving Access to a Full Suite of Differentially Substituted Phthalocyanine‐Porphyrin Hybrids

Abstract

Phthalocyanines and porphyrins are often the scaffolds of choice for use in widespread applications. Synthetic advances allow bespoke derivatives to be made, tailoring their properties. The selective synthesis of unsymmetrical systems, particularly phthalocyanines, has remained a significant unmet challenge. Porphyrin‐phthalocyanine hybrids offer the potential to combine the favorable features of both parent structures, but again synthetic strategies are poorly developed. Here we demonstrate strategies that give straightforward, controlled access to differentially substituted meso‐aryl‐tetrabenzotriazaporphyrins by reaction between an aryl‐aminoisoindolene (A) initiator and a complementary phthalonitrile (B). The choice of precursors and reaction conditions allows selective preparation of 1:3 Ar‐ABBB and, uniquely, 2:2 Ar‐ABBA functionalized hybrids.

Electrochromic Smart Window Based on Transition-Metal Phthalocyanine Derivatives

“…21,22 This approach addresses the solubility issue by adding transition metals at the center of the planar structure of the Pc ring, which increases the overall productivity. 15,16,23,24 Additionally, these Pc materials are readily available, which makes them suitable for commercial applications. These compounds have exhibited color changes upon the application of electric fields, with adsorption in the near-infrared region (NIR).…”

“…In this paper, we propose a novel synthetic method for modifying conventional Pc materials by adopting a quaternary tert -butyl substitution using zinc and cobalt Pc monomers. Stable electronic devices are fabricated by using the prepared Pc materials with EC properties. , This approach addresses the solubility issue by adding transition metals at the center of the planar structure of the Pc ring, which increases the overall productivity. ,,, Additionally, these Pc materials are readily available, which makes them suitable for commercial applications. These compounds have exhibited color changes upon the application of electric fields, with adsorption in the near-infrared region (NIR) .…”

“…A typical Pc consists of four isoindole units in a planar macrocyclic conjugated structure with a hole at the center that favors excellent stability along with a wide range of applications. , By introducing different metal centers at the hole, such as lutecium, cerium, and other rare earth elements, the energy level of the metal Pc compounds can be effectively modulated to achieve outstanding EC properties. , For instance, hybrid Pc rare earth complexes are a new class of molecular conductors that have good photoelectric conversion and are widely used as liquid crystals and applications involving other functional materials . The Pcs are easy to process and show good stability and fast response behavior, as they are compounds with a unique conjugated structure which facilitates the import of inorganic metal ions into the center of organic materials …”

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

“…The major drawback of this method is that it usually requires high temperature, which shifts the different equilibria towards the formation of a highly conjugated macrocycle, but does not allow the development of chemoselective conditions that lead to the formation of Pc rings containing different chemical functionalities at the constituent isoindoles in a controlled fashion. Some approaches have been addressed to control the cross-reactivity between different phthalonitrile units, using steric constrictions, 11–15 by preorganization of phthalonitrile units, 16–20 by sequential assembly, 21–26 or even using other types of precursors with complementary reactivity. 27–31 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.…”

Convenient syntheses of phthalocyanine and tetrabenzotriazaporphyrin (TBTAP) mono-alkynes; unhindered building blocks for click chemistry and beyond

“…In the last decades, our group and others have developed and studied new synthetic routes, significantly overcoming the initial issues [8][9][10][11][12][13][14][15][16][17][18][19]. Most recently we have disclosed additional control in the synthesis of TBTAPs that permits direct access to meso-aryl 3:1 (ABBB-Ar) and 2:2 (ABBA-Ar) derivatives [20]. Symmetry in the macrocycle core is intrinsically reduced by exchange of a single nitrogen bridge but, importantly, any meso-phenyl substituent lies perpendicular to the core such that further modification at this site has only marginal impact and the properties of the core are therefore preserved.…”