Convenient synthetic route of versatile 21-monothiatetraphenylporphyrins of the A4 and AB3 type

Rational enhancement of the energy barrier of bis(tetrapyrrole) dysprosium SMMs via replacing atom of porphyrin core

“… 7 – 12 However, core-modified porphyrins, interesting porphyrin isomers with the basic porphyrin framework preserved and at least one of the inner pyrrole nitrogen atoms replaced by another heteroatom, have never been incorporated into the sandwich complexes since they were first reported, in 1971. 13 In the present paper, the core-modified porphyrins HOTBPP and HSTBPP [HOTBPP = 5,10,15,20-(4- tert -butyl)phenyl-21-oxaporphyrin, HSTBPP = 5,10,15,20-(4- tert -butyl)phenyl-21-thiaporphyrin] were prepared by a modified procedure of a published pathway 14 (for details, please see the ESI † ). Similar to their mixed (phthalocyaninato)(porphyrinato) rare earth double-decker analogues, core-modified porphyrin-containing mixed ring dysprosium double-decker complexes Dy III (Pc)(XTBPP) [X = O ( 1 ), S ( 2 )], Scheme 1 , were also synthesized by reaction of the half-sandwich compound Dy(Pc)(acac) (acac = acetylacetonate) with metal-free core-modified porphyrin.…”

“…The core-modified porphyrins HOTBPP and HSTBPP, as well as their corresponding precursors, were also prepared according to a published procedure. 14 Unless otherwise noted, all other reagents and solvents were used as received.…”

Carbaporphyrinoid Systems

“…76,77 In addition, condensation of 31 with pyrrole and aromatic aldehydes in the presence of boron trifluoride etherate, followed by oxidation with DDQ, afforded the thiaporphyrins (33). 78,79 The same strategies can be applied to the preparation of oxa-, selena-, and telluraporphyrins. 80−87 Furthermore, this approach has been successfully utilized in the preparation of carbaporphyrinoid systems such as benziporphyrins.…”

“…For instance, thiophene dicarbinol 31 reacted with pyrrole in refluxing propionic acid to give dithiaporphyrin ( 32 ) (Scheme ). , In addition, condensation of 31 with pyrrole and aromatic aldehydes in the presence of boron trifluoride etherate, followed by oxidation with DDQ, afforded the thiaporphyrins ( 33 ). , The same strategies can be applied to the preparation of oxa-, selena-, and telluraporphyrins. − Furthermore, this approach has been successfully utilized in the preparation of carbaporphyrinoid systems such as benziporphyrins. , Mixed condensations of pyrrole, azulene, and aromatic aldehydes have also been applied to the synthesis of tetraarylazuliporphyrins. − …”

Synthesis of carboxylate functionalized A3B and A2B2 thiaporphyrins and their application in dye-sensitized solar cells

“…[14][15][16][17][18][19] A variety of mono-functionalized thiaporphyrins have been reported in the literature, 20,21 but the synthesis of carboxyl functionalized thiaporphyrins is quite rare. 22 Although these thiaporphyrins possess interesting optical properties, surprisingly their use in DSSCs is very uncommon. 23 Following our interest in thiaporphyrins and their metal complexes, 24,25 we have recently shown that these heteroporphyrins can be successfully applied as sensitizers in DSSCs.…”