Porphyrin-fullerene linked molecules

The photoinduced electron-transfer dynamics has also been examined for a series of porphyrin-fullerene-linked molecules with the same spacer employed for Fc-ZnP-H2P-C6o ZnP-Ceo (edge-to-edge distance Ree = 11-9 A), Fc-ZnP-Ceo (Ree = 30.3 A) and ZnP-H2P-Ceo (Ree = 30.3 A), shown in Chart 1 [53]. The driving force dependence of the electron-transfer rate constants ( et) of these dyad, triads, and tetrad molecules is shown in Fig. 3, where log et is plotted against the driving force (-AGet) [47]. 

The long lifetime and high quantum yield of the CS state of these donor-fullerene linked molecules seem to be efficient charge-generation species in the photoactive devices. A photoelectrochemical cell has been developed using a gold electrode which is covered by self-assembled mono-layers of porphyrin- Qo dyad with S-Au interaction [137]. 

Recently, photochemical and photoelectrochemical properties of fullerene (Cto) have been widely studied [60]. Photoinduced electron-transfer reactions of donor-Qo linked molecules have also been reported [61-63]. In a series of donor-Cfio linked systems, some of the compounds show novel properties, which accelerate photoinduced charge separation and decelerate charge recombination [61, 62]. These properties have been explained by the remarkably small reorganization energy in their electron-transfer reactions. The porphyrin-Qo linked compounds, where the porphyrin moieties act as both donors and sensitizers, have been extensively studied [61, 62]. 

In addition to metal coordination bonds, hydrogen bondings, electrostatics, and 7T-7T interactions, the attractive interaction between the curved r-surface of a fullerene and the flat rr-surface of a porphyrin was recently reported [8,9]. When the fullerene and the porphyrin were linked covalently in the single molecule (see 6), the two functions interacted with each other to form a supramolecular assembly in the solid state. In contrast to this divergent system, macrocycle 7 was prepared from the fused zinc porphyrins for the convergent interaction with specific guests. Since 7 had space to accommodate two fuUerenes, this kind of interaction operated well in the supramolecular assembly and moleciflar recognition systems. 

In a supramolecular approach to fullerene-porphyrin hybrids, the assembly of a rigidly connected dyad, in which a zinc tetraphenylporphyrin, Zn(TPP), is noncovalently linked to a C60 derivative via axial pyridine coordination to the metal, was reported [219-222]. Photo excitation of the dyad Zn-complex led to electron transfer with very long lifetimes of the charge-separated pairs, as revealed by optical spectroscopy and confirmed by time-resolved electron paramagnetic resonance spectroscopy. Accordingly, two different solvent-dependent pathways can be considered for the electron-transfer processes. Either the excitation of the porphyrin chromophore is followed by fast intramolecular electron transfer inside the complex, or alternatively the free porphyrin is excited undergoing intermolecular electron transfer when the acceptor molecules ap-... 

The best molecule mimicking multi-step electron-transfer processes in the photo synthetic reaction center so far reported is a ferrocene-meso, meso-linked porphyrin trimer-fullerene pentad [Fc-(ZnP)3-C60] in Fig. 13.16b, where the C60 and the ferrocene (Fc) are tethered at both the ends of (ZnP)3 (R = 46.9 A)... 

In 2002, a triad molecule including dithienylethene (DTE), porphyrin (P), and fullerene (DTE-P-C60) was first designed and synthesized as a photoinduced electron transfer (PET) switch by D. Gust et al. [33], as shown in Scheme 5. This molecule was synthesized by modified procedures reported literature Porphyrin chromophore was covalently linked to substituted dithienylethene by Sonogashira coupling reaction. Fullerene was introduced by the cycloaddition reaction of dyad aldehyde (dithienylethene-porphyrin aldehyde) with the fullerene and the N-methyl-glycine. 

A few other triads and more complex systems eonsisting of a porphyrin linked to two or more fullerene moieties have been reported [150, 159, 221]. The most complex to date is a tetraarylporphyrin linked to four fullerene moieties through double ester-containing bridges to the porphyrin meso aryl groups [151]. This molecule is rendered soluble in organie solvents via 16 twelve-carbon aliphatic chains. The porphyrin fluorescence is strongly quenehed by the attached Ceo moieties. 

---