Synthesis and Studies of Covalently Linked Porphyrin‐Expanded Heteroporphyrin Dyads

Abstract

Mono-functionalized core-modified sapphyrin (with a N 2 S 3 core) and smaragdyrin (with a N 4 O core) containing a mesoiodophenyl functional group were synthesized by following a [3+2] condensation approach using appropriate precursors. The mono-functionalized sapphyrin and smaragdyrin building blocks were used to synthesize the first examples of diphenyl ethyne bridged porphyrin-sapphyrin and porphyrin/ Zn II porphyrin-smaragdyrin dyads under mild Pd 0 -coupling conditions. The dyads are freely soluble in common organic

Synthesis, Characterization, and Electrochemistry of Open‐Chain Pentapyrroles and Sapphyrins with Highly Electron‐Withdrawing meso‐Tetraaryl Substituents

“…[12] Since then, sapphyrins have remained at opic of high interest, [13][14][15][16] in part because of their potential applicationsi nt he area of photodynamic therapy and their structurals imilarity to the well-known porphyrin and corrole macrocycles, [10,11,[17][18][19][20][21] and in part because of their unique properties as ar eceptor of neutraland anionic substrates. [22][23][24][25][26][27][28][29] Al arge number of studies have characterizedd ifferent sapphyrind erivatives, including b-alkylateds apphyrins, [30][31][32][33] coremodified sapphyrins with heteroatoms (O, S, or Se), [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] Nfused/N-confused sapphyrins, [51][52][53][54] and meso-tetraaryl-substituted sapphyrins. [55]…”

“…A large number of studies have characterized different sapphyrin derivatives, including β‐alkylated sapphyrins, core‐modified sapphyrins with heteroatoms (O, S, or Se), N‐fused/N‐confused sapphyrins, and meso ‐tetraaryl‐substituted sapphyrins . Sapphyrins containing four meso ‐aryl substituents can serve as favorable building blocks for the further design of molecules, which are similar to meso ‐aryl‐substituted porphyrins, whose redox properties and chemical reactions can be finely tuned .…”

Deprotonation Reactions and Electrochemistry of Substituted Open-Chain Pentapyrroles and Sapphyrins in Basic Nonaqueous Media

“…Sapphyrins, which are pentapyrrolic macrocycles containing one direct link and four bridging methane groups between five pyrrolic subunits, have attracted a great deal of research interest over the past decade, − in part because of their structural similarity to porphyrins and corroles, and in part because of their potential applications as photosensitizers for photodynamic therapy, magnetic resonance imaging contrasting agents, − and macrocyclic receptors for the transport of neutral and anionic substrates. − The most often characterized sapphyrins have contained core-modified macrocycles with O, S, or Se heteroatoms − but N-fused and N-confused macrocycles − as well as β-pyrrole substituted − and meso -substituted sapphyrin macrocycles have also been described in the literature. − …”

Synthesis and Studies of Mono‐functionalized Telluradithiasapphyrins and Covalently Linked Porphyrin‐ Telluradithiasapphyrin Dyads

“…Although extensive literature available on O, S and Se containing porphyrinoids, [11–14] the chemistry of Te containing porphyrinoids is remained limited due to inaccessibility of suitable precursors and inherent instability associated with Te containing porphyrinoids. For example, several multiporphyrin arrays containing oxa‐ and thiaporphyrins have been reported [15–18] but to the best of our knowledge, there is no report on telluraporphyrinoid containing multiporphyrin arrays. Recently, our group reported synthesis of tellurophene containing porphyrins and expanded porphyrins [3–7] .…”