Photoinduced Energy and Electron Transfer in Phenylethynyl‐Bridged Zinc Porphyrin–Oligothienylenevinylene–C60 Ensembles

Donor–bridge–acceptor triad (Por‐2TV‐C₆₀) and tetrad molecules ((Por)₂‐2TV‐C₆₀), which incorporated C₆₀ and one or two porphyrin molecules that were covalently linked through a phenylethynyl‐oligothienylenevinylene bridge, were synthesized. Their photodynamics were investigated by fluorescence measurements, and by femto‐ and nanosecond laser flash photolysis. First, photoinduced energy transfer from the porphyrin to the C₆₀ moiety occurred rather than electron transfer, followed by electron transfer from the oligothienylenevinylene to the singlet excited state of the C₆₀ moiety to produce the radical cation of oligothienylenevinylene and the radical anion of C₆₀. Then, back‐electron transfer occurred to afford the triplet excited state of the oligothienylenevinylene moiety rather than the ground state. Thus, the porphyrin units in (Por)‐2TV‐C₆₀ and (Por)₂‐2TV‐C₆₀ acted as efficient photosensitizers for the charge separation between oligothienylenevinylene and C₆₀.     

Stepwise charge separation and charge recombination in ferrocene-meso,meso-linked porphyrin dimer-fullerene triad

A meso,meso-linked porphyrin dimer [(ZnP)(2)] as a light-harvesting chromophore has been incorporated into a photosynthetic multistep electron-transfer model for the first time, including ferrocene (Fc), as an electron donor and fullerene (C(60)) as an electron acceptor to construct the ferrocene-meso,meso-linked porphyrin dimer-fullerene system (Fc-(ZnP)(2)-C(60)). Photoirradiation of Fc-(ZnP)(2)-C(60) results in photoinduced electron transfer from the singlet excited state of the porphyrin dimer [(1)(ZnP)(2)] to the C(60) moiety to produce the porphyrin dimer radical cation-C(60) radical anion pair, Fc-(ZnP)(2)(*+)-C(60)(*-). In competition with the back electron transfer from C(60)(*-) to (ZnP)(2)(*+) to the ground state, an electron transfer from Fc to (ZnP)(2)(*+) occurs to give the final charge-separated (CS) state, that is, Fc(+)-(ZnP)(2)-C(60)(*-), which is detected as the transient absorption spectra by the laser flash photolysis. The quantum yield of formation of the final CS state is determined as 0.80 in benzonitrile. The final CS state decays obeying first-order kinetics with a lifetime of 19 micros in benzonitrile at 295 K. The activation energy for the charge recombination (CR) process is determined as 0.15 eV in benzonitrile, which is much larger than the value expected from the direct CR process to the ground state. This value is rather comparable to the energy difference between the initial CS state (Fc-(ZnP)(2)(*+)-C(60)(*-)) and the final CS state (Fc(+)-(ZnP)(2)-C(60)(*-)). This indicates that the back electron transfer to the ground state occurs via the reversed stepwise processes,that is, a rate-limiting electron transfer from (ZnP)(2) to Fc(+) to give the initial CS state (Fc-(ZnP)(2)(*+)-C(60)(*-)), followed by a fast electron transfer from C(60)(*-) to (ZnP)(2)(*+) to regenerate the ground state, Fc-(ZnP)(2)-C(60). This is in sharp contrast with the extremely slow direct CR process of bacteriochlorophyll dimer radical cation-quinone radical anion pair in bacterial reaction centers.     

Driving force and electronic coupling effects on photoinduced electron transfer in a fullerene-based molecular triad

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 (> or = 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-separate 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.     

High effectiveness of oligothienylenevinylene as molecular wires in Zn-porphyrin and C60 connected systems

Photoinduced energy transfer and electron transfer processes have been found between the excited singlet state of Zn-porphyrin and C(60) via an oligothienylenevinylene bridge depending on the length of the oligothiophene and solvent polarity.     

Energy transfer followed by electron transfer in a supramolecular triad composed of boron dipyrrin, zinc porphyrin, and fullerene: a model for the photosynthetic antenna-reaction center complex

The first example of a working model of the photosynthetic antenna-reaction center complex, constructed via self-assembled supramolecular methodology, is reported. For this, a supramolecular triad is assembled by axially coordinating imidazole-appended fulleropyrrolidine to the zinc center of a covalently linked zinc porphyrin-boron dipyrrin dyad. Selective excitation of the boron dipyrrin moiety in the boron dipyrrin-zinc porphyrin dyad resulted in efficient energy transfer (k(ENT)(singlet) = 9.2 x 10(9) s(-)(1); Phi(ENT)(singlet) = 0.83) creating singlet excited zinc porphyrin. Upon forming the supramolecular triad, the excited zinc porphyrin resulted in efficient electron transfer to the coordinated fullerenes, resulting in a charge-separated state (k(cs)(singlet) = 4.7 x 10(9) s(-)(1); Phi(CS)(singlet) = 0.9). The observed energy transfer followed by electron transfer in the present supramolecular triad mimics the events of natural photosynthesis. Here, the boron dipyrrin acts as antenna chlorophyll that absorbs light energy and transports spatially to the photosynthetic reaction center, while the electron transfer from the excited zinc porphyrin to fullerene mimics the primary events of the reaction center where conversion of the electronic excitation energy to chemical energy in the form of charge separation takes place. The important feature of the present model system is its relative "simplicity" because of the utilized supramolecular approach to mimic rather complex "combined antenna-reaction center" events of photosynthesis.     

Long-lived charge-separated state generated in a ferrocene-meso,meso-linked porphyrin trimer-fullerene pentad with a high quantum yield

A meso,meso-linked porphyrin trimer, (ZnP)3, as a light-harvesting chromophore, has been incorporated for the first time into a photosynthetic multistep electron-transfer model including ferrocene (Fc) as an electron donor and fullerene (C60) as an electron acceptor, to construct the ferrocene-meso,meso-linked porphyrin trimer-fullerene system Fc-(ZnP)3-C60. Photoirradiation of Fc-(ZnP)3-C60 results in photoinduced electron transfer from both the singlet and triplet excited states of the porphyrin trimer, 1(ZnP)3* and 3(ZnP)3*, to the C60 moiety to produce the porphyrin trimer radical cation-C60 radical anion pair, Fc-(ZnP)3*+-C60*-. Subsequent formation of the final charge-separated state Fc+-(ZnP)3-C60*- was confirmed by the transient absorption spectra observed by pico- and nanosecond time-resolved laser flash photolysis. The final charge-separated state decays, obeying first-order kinetics, with a long lifetime (0.53 s in DMF at 163 K) that is comparable with that of the natural bacterial photosynthetic reaction center. More importantly, the quantum yield of formation of the final charge-separated state (0.83 in benzonitrile) remains high, despite the large separation distance between the Fc+ and C60*- moieties. Such a high quantum yield results from efficient charge separation through the porphyrin trimer, whereas a slow charge recombination is associated with the localized porphyrin radical cation in the porphyrin trimer. The light-harvesting efficiency in the visible region has also been much improved in Fc-(ZnP)3-C60 because of exciton coupling in the porphyrin trimer as well as an increase in the number of porphyrins.     

Photochromic control of photoinduced electron transfer. Molecular double-throw switch

A molecular double-throw switch that employs a photochromic moiety to direct photoinduced electron transfer from an excited state donor down either of two pathways has been prepared. The molecular triad consists of a free base porphyrin (P) linked to both a C(60) electron acceptor and a dihydroindolizine (DHI) photochrome. Excitation of the porphyrin moiety of DHI-P-C(60) results in photoinduced electron transfer with a time constant of 2.3 ns to give the DHI-P(*)(+)-C(60)(*)(-) charge-separated state with a quantum yield of 82%. UV (366 nm) light photoisomerizes the DHI moiety to the betaine (BT) form, which has a higher reduction potential than DHI. Excitation of the porphyrin of BT-P-C(60) is followed by photoinduced electron transfer with a time constant of 56 ps to produce BT(*)(-)-P(*)(+)-C(60) in 99% yield. Isomerization of BT-P-C(60) back to DHI-P-C(60) may be achieved with visible light, or thermally. Thus, photoinduced charge separation originating from the porphyrin is reversibly directed down either of two different pathways by photoisomerization of the dihydroindolizine. The switch may be cycled many times.     

Intermolecular and intracomplex photoinduced electron transfer from planar and nonplanar metalloporphyrins to p-quinones

The rate constants of intermolecular photoinduced electron transfer from triplet excited states of metalloporphyrins to a series of p-benzoquinone derivatives in benzonitrile were determined to examine the effects of the driving force, the metal, and the conformational distortion of the porphyrin ring on the reorganization energies (λ) of electron transfer by laser flash photolysis. The λ values were evaluated from the determined rate constants on the basis of the Marcus theory of electron transfer. The λ values of planar metalloporphyrins, [Al(TPP)(PhCOO)] and [Zn(TPP)] (TPP(2-)=tetraphenylporphyrin dianion), are approximately the same, but they are 0.27 eV smaller than those of the corresponding nonplanar (saddle-distorted) metalloporphyrins [Al(DPP)(PhCOO)] and [Zn(DPP)] (DPP(2-)=dodecaphenylporphyrin dianion) when they are compared for the same driving force of photoinduced electron transfer. The axial ligand PhCOO(-) of [Al(TPP)](+) and [Al(DPP)](+) was replaced by anthraquinone-2-carboxylate (AqCOO(-)) to afford the electron donor-acceptor complexes [Al(TPP)(AqCOO)] and [Al(DPP)(AqCOO)], respectively. The X-ray crystal structure of [Al(TPP)(AqCOO)] revealed strong coordination of AqCOO(-) to the Al(3+) ion of [Al(TPP)](+) and the existence of π-π interactions between AqCOO(-) and the porphyrin ring. In the case of the saddle-distorted [Al(DPP)(AqCOO)], however, the AqCOO(-) moiety is nearly perpendicular to the porphyrin ring. The photodynamics of intracomplex photoinduced electron transfer from the singlet excited state of [Al(TPP)](+) and [Al(DPP)](+) to the AqCOO(-) moiety were also examined in comparison with the intermolecular photoinduced electron-transfer reactions, and the determined rate constants were evaluated in light of the Marcus theory of electron transfer to reveal that the electron transfer is adiabatic in each case.     

卟啉-噁二唑二元体系光诱导能量及电子传递研究

以5-对氨基苯基-10,15,20-三苯基卟啉及2-苯基-5-(对氨基苯基)-1,3,4-噁二唑为原料合成了系列卟啉-噁二唑二元化合物, 其结构通过¹H NMR, ESI-MS, IR, UV-Vis确定. 对合成化合物进行光谱性能测定, 结果表明, 在卟啉与噁二唑混合体系中, 存在着卟啉激发态分子向噁二唑基态分子的分子间电子传递过程, 导致卟啉激发态的荧光猝灭; 在卟啉-噁二唑二元体系中, 315 nm激发下发生了由激发态噁二唑基团至卟啉基团的能量传递, 导致噁二唑基团荧光猝灭, 卟啉基团荧光增强. 420 nm激发下不存在分子内卟啉基团向噁二唑基团的电子回传竞争; 电化学性能测定进一步表明从噁二唑基团向卟啉基团的电子传递是可能的. 因此卟啉-噁二唑二元化合物可能作为一种模型, 模拟光合作用中电子给体至叶绿素之间的电子传递过程.     

Electronic and fluorescence spectral studies of a novel porphyrin-polypyridyl ruthenium(II) hybrid linked by a butyl chain

The electronic and fluorescence spectroscopic properties of a novel porphyrin-polypyridyl ruthenium(II) hybrid, [C(4)-TPP-(ip)Ru(phen)(2)](ClO(4))(2) (TPP=5,10,15,20-tetraphenylporphyrin, ip=imidazo[4,5-f][1,10]phenanthroline and phen=1,10-Phenanthroline), in which a polypyridyl ruthenium(II) moiety is linked to a porphyrin moiety by a butyl chain have been investigated and compared to its corresponding reference compounds. The studies of electronic absorption spectra have shown that there is an electronic interaction between the porphyrin moiety and the polypyridyl ruthenium(II) moiety in the hybrid. It can be found that intramolecular photoinduced electron and energy transfer processes may occur in the hybrid from the fluorescence spectra. When exciting in Soret band and Q band of porphyrin, the fluorescence quenching of the porphyrin moiety of the hybrid takes place due to electron transfer from the lowest singlet excited state (S(1)) to the appended polypyridyl rutherium(II) moiety, while the decay of S(2) (the second-excited singlet state) of the porphyrin moiety is mainly contributed to internal conversion to S(1). When exciting in MLCT band of the polypyridyl ruthenium(II) moiety, fluorescence corresponding to the polypyridyl ruthenium(II) moiety is quenched by intramolecular energy transfer from (3)MLCT of the ruthenium moiety to the lowest-energy triplet state localized on the porphyrin moiety.     

Fullerene- and pyromellitdiimide-appended tripodal ligands embedded in light-harvesting porphyrin macrorings

Three new tripyridyl tripodal ligands appended with either fullerene or pyromellitdiimide moieties, named C(60)-s-Tripod, C(60)-l-Tripod, and PI-Tripod, were synthesized and introduced into a porphyrin macroring N-(1-Zn)(3) (where 1-Zn = trisporphyrinatozinc(II)). From UV-vis absorption and fluorescence titration data, the binding constants of C(60)-s-Tripod, C(60)-l-Tripod, and PI-Tripod with N-(1-Zn)(3) in benzonitrile were estimated to be 3 × 10(8), 1 × 10(7), and 2 × 10(7) M(-1), respectively. These large binding constants denote multiple interactions of the ligands to N-(1-Zn)(3). The binding constants of the longer ligand (C(60)-l-Tripod) and the pyromellitdiimide ligand (PI-Tripod) are almost the same as those without the fullerene or pyromellitdiimide groups, indicating that they interact via three pyridyl groups to the porphyrinatozinc(II) coordination. In contrast, the larger binding constants and the almost complete fluorescence quenching in the case of the shorter ligand (C(60)-s-Tripod) indicate that the interaction with N-(1-Zn)(3) is via two pyridyl groups to the porphyrinatozinc(II) coordination and a π-π interaction of the fullerene to the porphyrin(s). The fluorescence of N-(1-Zn)(3) was quenched by up to 80% by the interaction of C(60)-l-Tripod. The nanosecond transient absorption spectra showed only the excited triplet peak of the fullerene on selective excitation of the macrocyclic porphyrins, indicating that energy transfer from the excited N-(1-Zn)(3) group to the fullerenyl moiety occurs in the C(60)-l-Tripod/N-(1-Zn)(3) composite. In the case of PI-Tripod, the fluorescence of N-(1-Zn)(3) was quenched by 45%. It seems that the fluorescence quenching probably originates from electron transfer from the excited N-(1-Zn)(3) group to the pyromellitdiimide moiety.     

Spectral, electrochemical, and photophysical studies of a magnesium porphyrin-fullerene dyad

A covalently linked magnesium porphyrin-fullerene (MgPo-C60) dyad was synthesized and its spectral, electrochemical, molecular orbital, and photophysical properties were investigated and the results were compared to the earlier reported zinc porphyrin-fullerene (ZnPo-C60) dyad. The ab initio B3LYP/3-21G(*) computed geometry and electronic structure of the dyad predicted that the HOMO and LUMO are mainly localized on the MgP and C60 units, respectively. In o-dichlorobenzene containing 0.1 M (n-Bu)4NClO4, the synthesized dyad exhibited six one-electron reversible redox reactions within the potential window of the solvent. The oxidation and reduction potentials of the MgP and C60 units indicate stabilization of the charge-separated state. The emission, monitored by both steady-state and time-resolved techniques, revealed efficient quenching of the singlet excited state of the MgP and C60 units. The quenching pathway of the singlet excited MgP moiety involved energy transfer to the appended C60 moiety, generating the singlet excited C60 moiety, from which subsequent charge-separation occurred. The charge recombination rates, k(CR), evaluated from nanosecond transient absorption studies, were found to be 2-3 orders of magnitude smaller than the charge separation rate, k(CS). In o-dichlorobenzene, the lifetime of the radical ion-pair, MgPo*+-C60*-, was found to be 520 ns which is longer than that of ZnPo*+-C60*- indicating better charge stabilization in MgPo-C60. Additional prolongation of the lifetime of MgPo*+-C60*- was achieved by coordinating nitrogenous axial ligands. The solvent effect in controlling the rates of forward and reverse electron transfer is also investigated.     

Mimicking photosynthetic antenna-reaction-center complexes with a (boron dipyrromethene)3-porphyrin-C60 pentad

A highly efficient functional mimic of the photosynthetic antenna-reaction-center complexes has been designed and synthesized. The model contains a zinc(II) porphyrin (ZnP) core, which is connected to three boron dipyrromethene (BDP) units by click chemistry, and to a C(60) moiety using the Prato procedure. The compound has been characterized using various spectroscopic methods. The intramolecular photoinduced processes of this pentad have also been studied in detail with steady-state and time-resolved absorption and emission spectroscopic methods, both in polar benzonitrile and nonpolar toluene. The BDP units serve as the antennae, which upon excitation undergo singlet-singlet energy transfer to the porphyrin core. This is then followed by an efficient electron transfer to the C(60) moiety, resulting in the formation of the singlet charge-separated state (BDP)(3)-ZnP(·+) -C(60)(·-) , which has a lifetime of 476 and 1000 ps in benzonitrile and toluene, respectively. Interestingly, a slow charge-recombination process (k(CR)(t)=2.6×10(6) s(-1)) and a long-lived triplet charge-separated state (τ(CS)(T)=385 ns) were detected in polar benzonitrile by nanosecond transient measurements.     

Photonic switching of photoinduced electron transfer in a dithienylethene-porphyrin-fullerene triad molecule

A dithienylethene (DTE)-porphyrin (P)-fullerene (C(60)) triad molecule in which intramolecular photoinduced electron transfer is controlled by the photochromic DTE moiety has been prepared. Irradiation of the molecule with visible light gives the open form of the dithienylethene (DTEo). Excitation of the porphyrin gives DTEo-(1)P-C(60), which undergoes photoinduced electron transfer with a time constant of 25 ps to generate DTEo-P(.+)-C(60)(.-). Irradiation with ultraviolet light produces the closed form of the dithienylethene (DTEc). Excitation of DTEc-P-C(60) yields DTEc-(1)P-C(60), whose porphyrin first excited singlet state is quenched in 2.3 ps by singlet-singlet energy transfer to DTEc, generating (1)DTEc-P-C(60) and precluding significant photoinduced electron transfer. Such highly reversible photonically controlled intramolecular photoinduced electron transfer may eventually be useful in the design of photonic or optoelectronic devices.     

Formation of a hybrid compound composed of a saddle-distorted Tin(IV)-porphyrin and a Keggin-type heteropolyoxometalate to undergo intramolecular photoinduced electron transfer

Nonplanar Sn(IV)-porphyrin complexes, [Sn(TMPP(Ph)(8))-Cl(2)] (1) and [Sn(TMPP(Ph)(8))(OMe)(2)] (2) (TMPP(Ph)(8): 5,10,15,20-tetrakis(4-methoxyphenyl)-2,3,7,8,12,13,17,18-octaphenylporphyrinato), were prepared and characterized by spectroscopic and electrochemical methods together with X-ray crystallography. Variable-temperature (1)H NMR study revealed that the coordination of the methoxo ligand of 2 is weak enough in solution to enhance the axial ligand exchange with a Keggin-type phosphotungstate (α-[PW(12)O(40)](3-)) due to the steric stress between the axial methoxo ligand and the peripheral phenyl groups of the porphyrin ligand. The formation of a novel 1:1 donor-acceptor complex, [Sn(TMPP(Ph)(8))(OMe)(α-[PW(12)O(40)])](2-) (4) was confirmed by (1)H NMR and UV-vis spectral titrations, and also by MALDI-TOF-MS measurements. Electrochemical measurements for the donor-acceptor complex in PhCN revealed that the Sn(IV)-TMPP(Ph)(8) moiety acts as an electron donor and the α-[PW(12)O(40)](3-) moiety acts as an electron acceptor and that the energy level of the electron-transfer (ET) state of the 1:1 complex (1.17 eV) is lower than that of the triplet excited states of the SnTMPP(Ph)(8) complex (1.31 eV). Femtosecond and nanosecond laser flash photolysis measurements indicate that intersystem crossing from the singlet excited sate to the triplet excited state occurs followed by intramolecular photoinduced electron transfer from the triplet excited state of the Sn(IV)-TMPP(Ph)(8) moiety to the α-[PW(12)O(40)](3-) moiety in the 1:1 complex in benzonitrile.     

Light-harvesting supramolecular porphyrin macrocycle accommodating a fullerene-tripodal ligand

Trisporphyrinatozinc(II) (1-Zn) with imidazolyl groups at both ends of the porphyrin self-assembles exclusively into a light-harvesting cyclic trimer (N-(1-Zn)(3)) through complementary coordination of imidazolyl to zinc(II). Because only the two terminal porphyrins in 1-Zn are employed in ring formation, macrocycle N-(1-Zn)(3) leaves three uncoordinated porphyrinatozinc(II) groups as a scaffold that can accommodate ligands into the central pore. A pyridyl tripodal ligand with an appended fullerene connected through an amide linkage (C(60)-Tripod) was synthesized by coupling tripodal ligand 3 with pyrrolidine-modified fullerene, and this ligand was incorporated into N-(1-Zn)(3). The binding constant for C(60)-Tripod in benzonitrile reached the order of 10(8) M(-1). This value is ten times larger than those of pyridyl tetrapodal ligand 2 and tripodal ligand 3. This behavior suggests that the fullerene moiety contributes to enhance the binding of C(60)-Tripod in N-(1-Zn)(3). The fluorescence of N-(1-Zn)(3) was almost completely quenched (approximately 97 %) by complexation with C(60)-Tripod, without any indication of the formation of charge-separated species or a triplet excited state of either porphyrin or fullerene in the transient absorption spectra. These observations are explained by the idea that the fullerene moiety of C(60)-Tripod is in direct contact with the porphyrin planes of N-(1-Zn)(3) through fullerene-porphyrin pi-pi interactions. Thus, C(60)-Tripod is accommodated in N-(1-Zn)(3) with a pi-pi interaction and two pyridyl coordinations. The cooperative interaction achieves a sufficiently high affinity for quantitative and specific introduction of one equivalent of tripodal guest into the antenna ring, even under dilute conditions ( approximately 10(-7) M) in polar solvents such as benzonitrile. Additionally, complete fluorescence quenching of N-(1-Zn)(3) when accommodating C(60)-Tripod demonstrates that all of the excitation energy collected by the nine porphyrins migrates rapidly over the macrocycle and then converges efficiently on the fullerene moiety by electron transfer.     

富勒烯(C60／C70)与N，N，N’，N’-四-(对甲苯基)-4，4’-二胺-1，1’-二苯硒醚(TPDASe)间光诱导电子转移过程的激光光解研究

富勒烯(C60／C70)与N，N，N’，N’-四-(对甲苯基)-4，4’-二胺-1，1’-二 苯硒醚(TPDASe)间在激光光诱导条件下，发生了分子间的电子转移过程．在可见- 近红外区(600-1200nm)，观测到了TPDASe阳离子自由基、富勒烯(C60／C70)激发三 线态和阴离子自由基，在苯腈溶液中，观测瞬态谱测定了电子从TPDASe转移到富勒 烯(C60／C70)激发三线态的量子转化产率(Φet^T)和电子转移常数(Ket)．     

Photoinduced long-lived charge separation in a tetrathiafulvalene-porphyrin-fullerene triad detected by time-resolved electron paramagnetic resonance

Photoinduced electron transfer has been observed in a molecular triad, consisting of a porphyrin (P) covalently linked to a tetrathiafulvalene (TTF) and a fullerene derivative (C(60)), in the different phases of the liquid crystal E-7 and in a glass of 2-methyltetrahydrofuran (2-MeTHF) by means of time-resolved electron paramagnetic resonance (EPR) spectroscopy. In both solvents, an EPR signal observed immediately after excitation has been assigned to the radical pair TTF(*+)-P-C(60)(*-), based on its magnetic interaction parameters and spin polarization pattern. In the 2-MeTHF glass and the crystalline phase of E-7, the TTF(*+)-P-C(60)(*-) state is formed from the TTF-(1)P-C(60) singlet state via an initial TTF-P(*+)-C(60)(*-) charge-separated state. Long-lived charge separation ( approximately 8 mus) for the singlet-born radical pair is observed in the 2-MeTHF glass at cryogenic temperatures. In the nematic phase of E-7, a high degree of ordering in the liquid crystal is achieved by the molecular triad. In this phase, both singlet- and triplet-initiated electron transfer routes are concurrently active. At room temperature in the presence of the external magnetic field, the triplet-born radical pair (T)(TTF(*+)-P-C(60)(*-)) has a lifetime of approximately 7 mus, while that of the singlet-born radical pair (S)(TTF(*+)-P-C(60)(*-)) is much shorter (<1 mus). The difference in lifetimes is ascribed to spin dynamic effects in the magnetic field.     

Catalytic effects of dioxygen on intramolecular electron transfer in radical ion pairs of zinc porphyrin-linked fullerenes.

Dioxygen accelerates back electron transfer (BET) processes between a fullerene radical anion (C60) and a radical cation of zinc porphyrin (ZnP) in photolytically generated ZnP.+-C60.- and ZnP.+-H2P-C60.- radical ion pairs. The rate constant of BET increases linearly with increasing oxygen concentration without, however, forming reactive oxygen species, such as singlet oxygen or superoxide anion. When ferrocene (Fc) is used as a terminal electron donor moiety instead of ZnP (i.e., Fc-ZnP-C60), no catalytic effects of dioxygen were, however, observed for the BET in Fc+-ZnP-C60.-, that is, from C60.- to the ferricenium ion. In the case of ZnP-containing C60 systems, the partial coordination of O2 to ZnP.+ facilitates an intermolecular electron transfer (ET) from C60.- to O2. This rate-determining ET step is followed by a rapid intramolecular ET from O2.- to ZnP.+ in the corresponding O2.--ZnP.+ complex and hereby regenerating O2. In summary, O2 acts as a novel catalyst in accelerating the BET of the C60.--ZnP.+ radical ion pairs.     

Artificial photosynthetic reaction centers: mimicking sequential electron and triplet-energy transfer.

An artificial photosynthetic reaction center consisting of a carotenoid (C), a dimesitylporphyrin (P), and a bis(heptafluoropropyl)porphyrin (P(F)), C-P-P(F) , and the related triad in which the central porphyrin has been metalated to give C-P(Zn)-P(F) have been synthesized and characterized by transient spectroscopy. These triads are models for amphipathic triads having a carboxylate group attached to the P(F) moiety; they are designed to carry out redox processes across lipid bilayers. Triad C-P-P(F) undergoes rapid singlet-singlet energy transfer between the porphyrin moieties, so that their excited states are in equilibrium. In benzonitrile, photoinduced electron transfer from the first excited singlet state of P and hole transfer from the first excited singlet state of P(F) yield the initial charge-separated state C-P(.) (+)-P(F) (.) (-). Subsequent hole transfer to the carotenoid moiety generates the final charge-separated state C(.) (+)-P-P(F) (.) (-), which has a lifetime of 1.1 mus and is formed with a quantum yield of 0.24. In triad C-P(Zn)-P(F) energy transfer from the P(Zn) excited singlet to the P(F) moiety yields C-P(Zn)-(1)P(F) . A series of electron-transfer reactions analogous to those observed in C-P-P(F) generates C(.) (+)-P(Zn)-P(F) (.) (-), which has a lifetime of 750 ns and is formed with a quantum yield of 0.25. Flash photolysis experiments in liposomes containing an amphipathic version of C-P(Zn)-P(F) demonstrate that the added driving force for photoinduced electron transfer in the metalated triad is useful for promoting electron transfer in the low-dielectric environment of artificial biological membranes. In argon-saturated toluene solutions of C-P-P(F) and C-P(Zn)-P(F) , charge separation is not observed and a considerable yield of triplet species is generated upon excitation of the porphyrin moieties. In both triads triplet energy localized in the P(F) moiety is channeled to the carotenoid chromophore by a triplet energy-transfer relay mechanism. Certain photophysical characteristics of these triads, including the sequential electron transfer and the triplet energy-transfer relay mechanism, are reminiscent of those observed in natural reaction centers of photosynthetic bacteria.