Di-phenyl porphyrins

Figure 14. Structure of ether-substituted di-phenyl porphyrins...

Figure 16. Structure of ester-substituted di-phenyl porphyrin with single lateral chain.

Figure 18. Structure of o-(p-nitrophenylsulfonyl)oxy-substituted Zn" di-phenyl porphyrin (R = C6H4-0-r7C7His or R = C6Hio-nC7H,s). Reprinted with permission from Wang, Q. M. Bruce, D. W. /. Chem. Soc., Chem. Commun. 1996, 2505.

Figure 17. Structure of ester-substituted di-phenyl porphyrins with two lateral chains (R = C6Hio-n-C7His or R = C6H4-0-n-CmH2m + i, m = 7,8.).

Nishitani et al. observed the tip-enhanced fluorescence of 8 nm thick meso-tetralds (3,5-di-tertiarybutyl-phenyl)porphyrin (H2TBPP) films on ITO with an Ag tip [38]. They reported that the fluorescence was enhanced by the locally confined electromagnetic field in the vicinity of the tip. The enhancement factor is evaluated to be larger than 2000. 

In 1989, the irradiation of (E,E)-2,4-hexadiene S3 sensitized by meso-porphyrin IX dimethyl ester led to the formation of cis-3,6-dimethyl-l,2-dioxene (62), which was the major product detected at — 78 °C in Freon 11 [69]. Endoperoxide 62 was purified under vacuum at 0.75 mmHg, and collected in a trap (98% isolated yield). Dienes that can adopt a cisoid conformation, such as 53 or ( , )-l,4-di phenyl butadiene, were photooxidized by the corresponding endoperoxides in high or quantitative yield in a suprafacial Diels-Alder reaction [60, 70], Dienes that cannot readily adopt cisoid conformations, such as (fc, Z)-2,4-hexadienes and (Z, Z)-2,4-hexadienes, lose their stereochemistry in the singlet oxygen [2 + 4]-cyclo-addition [60], (E,Z)- and (Z,Z)-dienes give a complex mixture of hydroperoxides and aldehydes, which suggests the intervention of intermediate zwitterions or 1,4-diradicals [71]. 

The same principle of nucleophilic substitution has been applied to prepare other derivatives. With porphyrins like meso-tetrakis(pentafluoro-phenyl)porphyrin 48, the reactivity of the para-fluoro atoms towards nucleo-phihc substitutions has been well established. Thus the galactoconjugate porphyrin derivative 49b has been obtained from the reaction of porphyrin 48 with l,2 3,4-di-0-isopropylidene-a-D-galactopyranose (Scheme 7). Acidic... 

Due to the disc-like geometry of the porphyrin macrocycle, discotic mesophases have generally been the most common for porphyrin liquid-crystalline materials. The first porphyrin liquid crystals featuring rod-like calamitic mesophases were described by Bruce and coworkers using substituted 5,15-di(phenyl) zinc porphyrin complexes as the basic molecular building block.The first materials... 

Recently, a metaloporphyrin MOF was successfully used to pyrolytically synthesize a highly active ORR catalyst. In contrast to other Fe-based MOFs, the pyrolysis at 700-1000 °C of the polymerized Fe h5 10,15,20-tetrakis-(3,5-di-thio-phen-2-yl-phenyl)porphyrin... 

In order to prepare asymmetric meso-porphyrinylsugar derivatives (mono-, di- and tri-glycosylarylporphyrins), pyrrole was condensed with a mixture of glycosylated and nonglycosylated aldehydes.17,21,24,44 46 Several porphyrinylsugar derivatives were prepared by this synthetic methodology. The saccharide unit can be directly linked to the porphyrin macrocycle 35-50 or separated from the phenyl group by a spacer, such as in the case of derivative 51-53 shown below (Fig. 4). 

Crusats, J., Claret, J., Di ez-Perez, I., et al. (2003). Chiral shape and enantioselective growth of colloidal particles of self-assembled meso-tetra(phenyl and 4-sulfonatophenyl)porphyrins. Chem. Commun., 13, 1588-9. 

Jung and co-workers investigated both (a) the interaction of diporphyrins (3,5-di(tert-butyl)phenyl substituents) with C o molecules on Ag(lll) surfaces [165] and (b) single copper-octaethyl porphyrins on top of thin NaCl islands on metals [166] with STM at room temperature in ultrahigh vacuum. In the latter case, the electronic structure of the porphyrin was different on the metal surfaces when compared to that on thin layers of NaCl. 

In Fig. 6.38(a) are depicted the correlated NHN-hydrogen bond coordinates (Table 6.5) of porphyrin, of TTAA, porphycene, of the pyrazoles discussed in the previous section, as well as the calculated values of the transition states of porphyrin [65] and of its mono-deprotonated anion [81]. Also the data point of the double proton transfer in the cyclic N,N -di-(p-F-phenyl)amidine dimer was added, which is discussed in the next section as it involves a hydrogen bond pre-equilibrium and a coupling to the reorientation ofthe aryl groups. 

The metal-free condensation of fr(2-formylphenyl)telluride with a series of diamines afforded the macrocyclic tellurium Schiff base macrocycles attempted complexation with Pt(II) and Hg(II) afforded transmetalated products <04JOM1452>. Reduction of the Schiff base components of these chalcogenaza macrocycles gave rise to more robust and flexible macrocycles, which form the desired Pd(II) Tie,iV,jV, Tie-complex <04CC322>. The related Se-derivatives are also therein reported. 5,10-Diphenyl-15,20-di(4-methoxyphenyl)-21-tellura-porphyrin was prepared (18%) by the acid-catalyzed condensation of 2,5-6w(l-phenyl-l-hydroxymethyl)tellurophene, pyrrole, and 4-methoxybenzaldehyde, followed by oxidation with /j-chloranil <04OM4513>. 

Fig.29 a Di-zinc(II) bis-porphyrin receptor complex with 5,10-dipyridyl porphyrin (substituents on the phenyl groups omitted) [93] b X-ray structure of the sandwich-complex 36 reprinted with permission from [36], Copyright (2002) American Chemical Society... 

Advantages of the push-pull MP design in the small-molecule BHJ SCs were evaluated using two similar trans-2B2C ZnPs. Two alkoxy mc o-substituents were introduced to increase solubiUly of the porphyrins while others, vis., 3-hexylthienyl-terminated 2,1,3-benzothiadiazole, for enhancement of the intramolecular charge transfer (Scheme 54). Two compounds were synthesized, namely, 5,15-bis (7-(4-hexyl-thiophen-2-yl)-2,1,3-benzothiadiazole-4-yl-ethynyl)- 10,20-bis(3,5-di (dodecyloxy)-phenyl) ZnP (DHTBTEZP) and 5,15-bis(7-(4-hexyl-thiophen-2-yl)-2, l,3-benzothiadiazole-4-yl)-10,20-bis(3,5-di(dodecyloxy)-phenyl) ZnP (DHTBTZP) with the ethynyl- and phenyl-hnked acceptor moiety, respectively, (a and b, respectively, in Scheme 54) [119]. 

Carbodiimid.es N,N -Dicyclohexyl-carhodiimide Antipyrine Imidazole N,N -Car b onyld i-imidazole Hemato porphyrin Di-o-tolylguanidine 2,4-Diguanidino phenyl lauryl ether Fungi (Mold), Yeast Amino acid oxidase, Aspergillus oryzae enzyme, Chymotrypsin, Emulsin, Hog kidney enzyme, Isomerase, Papain, Pseudomonas extract... 

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