Tetrakis(tetrathiafulvalene–tetrathiacrown ether)porphyrazine Triads: Synthesis, Photophysical, and Electrochemical Properties

Abstract

A series of tetrakis(tetrathiafulvalene‐tetrathiacrown ether)porphyrazine triads with long and flexible aliphatic side‐chains at the periphery have been synthesized and characterized. Electrochemical investigations show two reversible four‐electron oxidation waves, one reversible one‐electron oxidation wave and two irreversible one‐electron reduction waves, which indicates that these triads are good π‐electron donors. Selected triad 4a reacted with 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) to form a charge‐transfer complex, which exhibits absorption bands at around 760 and 860 nm. Selected triads 4a and 5a bind silver(I) and mercury(II) ions. In the case of triad 4a, the addition of silver(I) ions led to dimerization of the triad, which fragmented to form monomeric 4:1 host–guest complexes when more than 2 equiv. of the metal ions were added. X‐ray scattering at room temperature showed that triad 5c is a highly ordered oblique columnar structure in the bulk state. The crystal structures of the precursors 3b,c were also determined by X‐ray diffraction analysis.

Discotic Liquid Crystals

“…Hou et al presented redox-active tetrathiafulvalene-thiacrown ether porphyrazine triads showing a Col ob phase. 545 In solution, a high tendency toward complexation of Ag + and Hg 2+ was observed, resulting in dimerization of the triad.…”

Dendrimeric Sulfanyl Porphyrazines: Synthesis, Physico‐Chemical Characterization, and Biological Activity for Potential Applications in Photodynamic Therapy

“…Porphyrazines that contain sulfanyl substituents reveal good solubility in common organic solvents and significant photocytotoxicities . Many years of research on sulfanyl porphyrazines led to the expansion of their periphery with various groups; for example, ether/thioether, calixarene, (tetrathiafulvalene)sulfanylethyl, 2′‐(4‐pyridoxy)ethyl, 1‐naphthylmethyl, 2′‐(ferrocenecarboxy)ethyl, and 4‐(4‐nitroimidazol‐1‐yl)butyl …”

“…[2][3][4][5] Porphyrazines that contain sulfanyl substituents revealg ood solubility in common organic solvents and significant photocytotoxicities. [6][7][8][9] Many years of research on sulfanyl porphyrazines led to the expansion of their periphery with various groups;f or example, ether/thioether, [10,11] calixarene, [12] (tetrathiafulvalene)sulfanylethyl, [13] 2'-(4-pyridoxy)ethyl, [14] 1-naphthylmethyl, [8] 2'-(ferrocenecarboxy)ethyl, [15] and 4-(4-nitroimidazol-1-yl)butyl. [16] The possibility to add and modify dendrimer substituents at the periphery of macrocyclic rings has been applieds of ar for porphyrins and phthalocyanines.…”

Synthesis and Properties of Norphthalocyanines Functionalized with a Tetrathiacrown Ether–Tetrathiafulvalene Substituent

“…Key precursor TTF-dicyanotetrathiacrown ether 2 was obtained according to previously reported procedures [ 14 ]. As shown in Scheme 1 , the mixed condensation of 1,2-dicyanobenzene (20 equiv) and derivative 2 (1 equiv) under classic Linstead macrocyclization conditions produced two phthalocyanine products, namely, the desired mono tetrathiafulvalene–tetrathiacrown ether Mg–norphthalocyanine 1 and Mg-phthalocyanine.…”