Preparation and Electrochemical Properties of 1,4,8,11,15,18,22,25‐Octalkylphthalocyanines Containing Four Trithiole Rings

Abstract

xylylenedithio)phthalocyanines 4a-d (alkyl = ethyl, butyl, octyl, and dodecyl) were prepared in moderate yields by treatment of 3,6-dialkyl-4,5-(o-xylylenedithio)phthalonitriles 3a-d with lithium in n-pentanol. Reductive removal of the four o-xylylene groups from 4b and 4c was performed with lithium/THF/ammonia, and the octathiolate anions generated were then treated with elemental sulfur to give the new phthalocyanines 6b and 6c, respectively, each containing four trithiole rings, after partial desulfurization and ring-contraction reactions of the corresponding phthalocyanines 5b and 5c. The structures of the phthalocyanines were determined by 1 H NMR spectroscopy and MALDI-TOF mass spec-

Optical limiters with improved performance based on nanoconjugates of thiol substituted phthalocyanine with CdSe quantum dots and Ag nanoparticles

“…Two major approaches of Pc thiolation were previously reported, namely the reaction of Pcs bearing terminal leaving groups with thiourea and the subsequent hydrolysis of the intermediate thiouronium salt 32,34,35 or the direct functionalization of Pcs with thiol-containing fragments. 31 Using the first approach, we started the synthesis of the target thiolated phthalocyanine 1 from the previously reported A 3 B-type ligand 2, which was shown to exhibit prominent NLO properties due to the low molecular symmetry.…”

Preparation, Structure Determination, and Electrochemical Properties of Bis{[1,4,8,11, 15,18,22,25‐octaethyl‐2,3,9,10,16,17,23,24‐octakis(methylthio)phthalocyaninato]titanium(IV)} Benzene‐1,2,4,5‐tetrathiolate

“…Two ethyl groups on the benzene ring positioned next to the two sulfur atoms are required to prepare compound 1 from 1,4‐diethylbenzene by way of diethyl‐1,2,3‐benzotrithiole as a precursor. It is expected that electron‐donating functional groups at the α‐positions of phthalocyanine cause the Q‐band to shift to a longer wavelength,11 and phthalocyanine with methylthio groups simplifies the structure of the double‐decker molecule compared with the benzylthio and xylylenedithio derivatives 10a,10b. Tetramerization and cyclization of phthalonitrile 2 upon treatment with lithium in n ‐pentanol at 115 °C for 1 h gave a green solid, which was filtered, dried, and purified by silica gel column chromatography to produce octaethyl‐octakis(methylthio)phthalocyanine ( 3 ) in 37 % yield.…”

Benzo-Annelated Cyclic Polysulfides

“…To prepare phthalocyanine with the trithiole ring, reductive removal of four o-xylylene groups from tetrakis(oxylylenedithio)phthalocyanines (43) was performed with lithium/THF/ammonia at -78 °C (Scheme 16) [30]. The octathiolate anions generated were then reacted with elemental sulfur to give new phthalocyanines (44) with one pentathiepin and three trithiole rings.…”

“…Titanocene polysulfide has been used as a sulfur transfer reagent, which reacted with 1,2bis(chlorosulfenyl)benzene (51) to produce the corresponding cyclic polysulfides (52), (53) and (54). Photolysis of benzobistrithiole (30) produced thianthrene (55) with two trithiole rings in low yield (Scheme 20). thianthrene by way of consecutive desulfurization, dimerization, and ring contraction [38,39].…”

“…Several novel trichalcogenolium radical cation salts 36(•+) were readily isolated in the one-electron oxidation of trichalcogenoles (36) with one equivalent NOPF 6 in ether-MeCN (Scheme 24 and Table 3) [28]. Benzobistrithiole (30) was oxidized using concentrated D 2 SO 4 , leading to generation of the radical cation 30(•+), which was verified by EPR spectroscopy (Scheme 25) [47]. The peak splitting suggests a partially spin delocalized system over both the benzene and trichalcogenole rings.…”