Synthesis of some mono, di, and trisubstituted tetraarylporphyrins

Anton, John A.; Loach, Paul A.

doi:10.1002/jhet.5570120326

Cited by 40 publications

(14 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5-(4-Carboxyphenyl)-15-(4-hydroxymethylphenyl)-10,20-bis(4methylphenyl)porphyrin (7). Porphyrin 6 (1.0 g, 1.32 mmol) (33,34) was dissolved in a mixture of 50 mL of trifluoroacetic acid and 150 mL of concentrated hydrochloric acid. The solution was heated to 80ЊC and stirred for 2 h. The mixture was allowed to come to room temperature and poured into chloroform containing 20% methanol.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Driving Force and Electronic Coupling Effects on Photoinduced Electron Transfer in a Fullerene-based Molecular Triad¶

Bahr

Kuciauskas

Liddell

et al. 2007

Photochemistry and Photobiology

View full text Add to dashboard Cite

Tuning thermodynamic driving force and electronic coupling through structural modifications of a carotene (C) porphyrin (P) fullerene (C60) molecular triad has permitted control of five electron and energy transfer rate constants and two excited state lifetimes in order to prepare a high‐energy charge‐separated state by photoinduced electron transfer with a quantum yield of essentially unity (≥96%). Excitation of the porphyrin moiety of C–P–C60 is followed by a combination of photoinduced electron transfer to give C–P·+–C60·− and singlet–singlet energy transfer to yield C–P–1C60. The fullerene excited state accepts an electron from the porphyrin to also generate C–P·+–C60·−. Overall, this initial state is formed with a quantum yield of 0.97. Charge shift from the carotenoid to yield C·+–P–C60·− is at least 60 times faster than recombination of C–P·+–C60·−, leading to the overall quantum yield near unity for the final state. Formation of a similar charge‐separated species from the zinc analog of the triad with a yield of 40% is also observed. Charge recombination of C·+–P–C60·− in 2‐methyltetrahydrofuran yields the carotenoid triplet state, rather than the ground state. Comparison of the results for this triad with those for related triads with different structural features provides information concerning the effects of driving force and electronic coupling on each of the electron transfer steps.

show abstract

Section: Methodsmentioning

confidence: 99%

“…Preparation of the porphyrin moiety began with the known 5,15-bis-(4-methoxycarbonylphenyl)-10,20-bis-(4-methylphenyl)porphyrin 6 (33,34). Hydrolysis of one ester group followed by reduction of the remaining ester with lithium aluminum hydride gave alcohol 7, which was oxidized to aldehyde 8 using manganese dioxide.…”

Section: Synthesismentioning

confidence: 99%

Driving Force and Electronic Coupling Effects on Photoinduced Electron Transfer in a Fullerene-based Molecular Triad¶

Bahr

Kuciauskas

Liddell

et al. 2007

Photochemistry and Photobiology

View full text Add to dashboard Cite

show abstract

“…Since our first report (1) of covalently-linked dimeric porphyrins, joined by amide linkages, a number of similar dimeric porphyrins with amide, ester, or ether linkages have been reported (2)(3)(4)(5)(6)(7)(8)(9)(10). That all of these systems employed the coupling of porphyrins, through these functional groups, results from the 'ready' availability of the porphyrin precursors and the ease of formation of amide, ester, and ether linkages.…”

mentioning

confidence: 99%

Synthesis of covalently-linked dimeric porphyrins

Paine¹,

Dolphin²

1978

Can. J. Chem.

View full text Add to dashboard Cite

DOLPHIN. Can. J. Chem. 56,1710(1978. Dimeric porphyrins covalently linked directly at their periphery (P,Pr-biporphyrins) or via a hydrocarbon chain (CH?),, where tt = 1-8, have been synthesized from the corresponding P,P'-linked bispyrroles. JOHN B. PAINE 111 et DAVID DOLPHIN. Can. J. Chem. 56,1710Chem. 56, (1978 Utilisant ies bispyrroles correspondants lies en P.P' cornme produits d e depart, on a synthetise les porphyrines dimkres liees d'une f a~o n covalente directernent & leur piriphirie (P.P' biporphyrines) ou par I'intermediaire d'une chaine hydrocar-bonee (CH?),, ou t~ = 1-8.[Traduit par le joul-nal]Since our first report (1) of covalently-linked dimeric porphyrins, joined by amide linkages, a number of similar dimeric porphyrins with amide, ester, or ether linkages have been reported (2-10). That all of these systems employed the coupling of porphyrins, through these functional groups, results from the 'ready' availability of the porphyrin precursors and the ease of formation of amide, ester, and ether linkages. However, once formed, such linkages have numerous disadvantages in that they generally lower the solubility (of systems which naturally have low solubilities), and increase the reactivity, and thereby decrease the stability. In addition the presence of extraneous functional groups complicates mechanistic and spectral studies on such systems.Whereas all previous syntheses of dimeric porphyrins consist of joining two preformed porphyrin entities in the final steps, our approach consists of constructing the covalent linkjrsr, and then building a porphyrin onto either end. To avoid the disadvantages of the linkages discussed above a synthesis has been developed where hydrocarbon chainlinked bispyrroles 1 are converted into the corresponding dimer porphyrins 7 where the hydrocarbon chain plays a passive role both chemically and electronically.Experimentally, the sequence depicted in Scheme 1 is facile to perform. The preparation of the bispyrroles 1 depends upon the length of the linking chain. When 17 = 0 the P,Pf-bipyrrole was prepared by Ullmann coupling (11) of the corresponding P-iodopyrrole 8 (R = I). For 11 = 1 the P,P'-dipyrromethane was prepared from 9 (R = H ) and acidified methanolic formaldehyde. For n > 5 acylation of 8 (R = H) or 9 (R = H ) with a diacid chloride (in methylene chloride -nitromethane a t 0°C with excess stannic chloride) gave the diketo bispyrroles 13 which were reduced to 1 with an excess of diborane. The diacid chlorides of succinic and glutaric acids could only be mono substituted, presumably owing to the propensity of the intermediate pyrrolyl keto acid chlorides 10c to cyclise to the five-and six-membered en01 lactones, which upon work u p gave the pyrrolyl keto acids 10a. These after esterification to the ethyl esters lob were reduced by diborane in ethyl acetate -tetrahydrofuran to lla, which were selectively saponified (carboxylalkyl sidechain esters saponify much faster than nuclear carboxylate esters which are vinylogous carbamates) to llb. These two carboxy...

show abstract

“…This compound was synthesized by the modified method of Anton and Loach [12]. A solution of 4methoxybenzaldehyde (4 ml.…”

Section: -(4-pyridyl)-101520-tri(4-methoxyphenyl)porphyrinmentioning

confidence: 99%

Novel porphyrin-labelled poly(N-isopropylacrylamides): syntheses from bromoalkyl-containing prepolymers and physicochemical properties

Avlasevich

Chevtchouk

Knyukshto

et al. 2000

J. Porphyrins Phthalocyanines

View full text Add to dashboard Cite

Novel water-soluble tetraarylporphyrin-labelled polymers have been synthesized by the reaction of bromoalkyl-containing poly(N-isopropylacrylamides) with 5-(4-pyridyl)-10,15,20-tri(4-methoxyphenyl) porphyrin. Corresponding Zn -porphyrin-containing polymers have also been prepared. Phase transition diagrams show that aqueous polymer solutions exhibit phase separation upon heating. Absorption spectra of the porphyrin-labelled polymers have been recorded in water and organic solvents. It is found that the absorption bands in aqueous polymer solutions are broadened and shifted bathochromically, the peak intensity of the Soret band in the polymer spectra being strongly lowered in water. Fluorescence properties of the polymers are briefly reported.

show abstract

Synthesis of some mono, di, and trisubstituted tetraarylporphyrins

Cited by 40 publications

References 14 publications

Driving Force and Electronic Coupling Effects on Photoinduced Electron Transfer in a Fullerene-based Molecular Triad¶

Driving Force and Electronic Coupling Effects on Photoinduced Electron Transfer in a Fullerene-based Molecular Triad¶

Synthesis of covalently-linked dimeric porphyrins

Novel porphyrin-labelled poly(N-isopropylacrylamides): syntheses from bromoalkyl-containing prepolymers and physicochemical properties

Contact Info

Product

Resources

About