Tetra-carboxyphenyl porphyrin

The macrocyclic effect can also be employed. MOF [Zrg04(0FI)4(tcpp-Fl2)3] (tcpp-H2 = tetra(carboxyphenyl) porphyrin. Chart 2) is constructed using unmetallated porphyrin square planar tectons. The MOF can be quantitatively metalled in an SCSC manner to form [Zrg04(0FI)4(tcpp-FeCl)3] by immersion in a DMF solution of FeCl3 at 100 °C. Interestingly, this MOF could not be formed directly using a premetallated H4tcppFeCl precursor. 

DCE interface in the presence of TPBCl [43,82]. The accumulation of products of the redox reactions were followed by spectrophotometry in situ, and quantitative relationships were obtained between the accumulation of products and the charge transfer across the interface. These results confirmed the higher stability of this anion in comparison to TPB . It was also reported that the redox potential of TPBCP is 0.51V more positive than (see Fig. 3). However, the redox stability of the chlorinated derivative of tetra-phenylborate is not sufficient in the presence of highly reactive species such as photoex-cited water-soluble porphyrins. Fermin et al. have shown that TPBCP can be oxidized by adsorbed zinc tetrakis-(carboxyphenyl)porphyrin at the water-DCE interface under illumination [50]. Under these conditions, the fully fluorinated derivative TPFB has proved to be extremely stable and consequently ideal for photoinduced ET studies [49,83]. Another anion which exhibits high redox stability is PFg- however, its solubility in the water phase restricts the positive end of the ideally polarizable window to < —0.2V [85]. 

Intercalation of tetra(4-carboxyphenyl)porphyrin (TPP-C) into the interlayer space of Zn-Al LDH, however, gave a different result [101]. The XRD pattern showed two peaks corresponding to interlayer spacings of 7.8 and 23.7 A. The 7.6-A spacing is attributed to the LDH in which the TPP-C molecules were arranged parallel to the plane of the host layers. Expansion of the layer to 23.7 A indicates that the plane of TPP-C was perpendicular to the plane of the Zn-Al LDH layers (Fig. 51) [101b],... 

One of the best studied families of porphyrins for use as metalloligands is comprised of metalated 7e50-tetra(p-carboxyphenyl)porphyrins (TCPPs). Several reviews have discussed the synthesis and properties of TCPP CPs and MOFs (38, 102, 103). As with other supramolecular structures, the structures of these TCPP MOFs are dictated by the geometries of their nodes. Typically, TCPP MOFs have two types of nodes the four-connected, approximately square-planar porphyrins, and the SBUs, which can have various geometries but... 

Cherian, S. and Wamser, C.C. (2000) Adsorption and photoactivity of tetra(4-carboxyphenyl)porphyrin (TCPP) on nanoparticulate Ti02. J. Phys. Chem. B, 104, 3624-3629. 

Dislcin-Posner. Y. Goldberg. I. From porphyrin sponges to porphyrin sieves A unique crystalline lattice of aquazinc tetra(4-carboxyphenyl)porphyrin with nanosized channels. Chem. Commun. 1999. 19. 1961-1962. 

Diskin-Posner. Y. Goldberg, I. Porphyrin sieves. Designing open networks of tetra(carboxyphenyl)poiphyrins by extended coordination through sodium ion auxiliaries. New J. Chem. 2001, 25. 899-904. 

The reactivity of three different Co(III) porphyrin complexes, Co (P), where P = TPPS, TMPyP, and TCPP = meso-tetra-(4-carboxyphenyl)-porphyrin, toward NO was studied spectroscopically and kinetically (126). The overall stoichiometry of these reactions described by Equation (13) clearly shows that the formation of the nitrosyl product, Co P)(NO ), involves consumption of two molecules of NO, whereby 1 mol of N02 is produced per mole of complex. 

Figure 11.4. Molecular structure of the various water-soluble porphyrins and chlorins studied by photoelectrochemistry at the hquid/hquid interfaces chlorin e-6, protoporphyrin IX (protoIX), Sn(IV) mero-tetra(4-carboxyphenyl) porphyrin dichloiide (SnTPPC), Zn(II) mer >-tetra(Ai-methyl-4-pyridinium) porphyrin (ZnTMPyP) and Zn(II) meso-tetra. (4-sulphonatophenyl) porphyrin (ZnTPPS). The Zn(II) derivatives of TPPC have also been extenively studied.

Jensen, H., J.J. Kakkassery, H. Nagatani, D.J. Fermfn, and H.H. Girault (2000). Photoinduced electron transfer at hquid/liquid interfaces. Part IV. Orientation and reactivity of zinc tetra(4-carboxyphenyl) porphyrin self-assembled at the water/1,2-dichloroethane junction. J. Am. Chem. Soc. 122, 10943-10948. 

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