Prashanth K. Poddutoori

Photoinduced Charge Separation in a Ferrocene−Aluminum(III) Porphyrin−Fullerene Supramolecular Triad†

Light-induced electron transfer is investigated in a ferrocene-aluminum(III) porphyrin-fullerene supramolecular triad (FcAlPorC(60)) and the constituent dyads (AlPorC(60) and FcAlPorPh). The fullerene unit (C(60)) is bound axially to the aluminum(III) porphyrin (AlPor) via a benzoate spacer, and ferrocene (Fc) is attached via an amide linkage to one of the four phenyl groups in the meso positions of the porphyrin ring. The absorption spectra and voltammetry data of the complexes suggest that the ground state electronic structures of the Fc, AlPor, and C(60) entities are not significantly perturbed in the dyads and triad. Time-resolved optical and transient electron paramagnetic resonance (EPR) data show that photoexcitation of the AlPorC(60) dyad results in efficient electron transfer from the excited singlet state of the porphyrin to fullerene, producing the charge-separated state AlPor(•+)-C(60)(•-). The fluorescence and transient EPR data also suggest that some energy transfer from the porphyrin to fullerene may occur. The lifetime of the radical pair AlPor(•+)-C(60)(•-) measured by transient absorbance spectroscopy is found to be 39 ns in o-dichlorobenzene at room temperature. At 200 K, transient EPR experiments place a lower limit of 5 μs on the radical pair lifetime. In the triad, the data suggest that excitation of the porphyrin gives rise to the charge-separated state Fc(•+)-AlPor-C(60)(•-) in two electron transfer steps. Photocurrent measurements demonstrate that both dyads and the triad have good photovoltaic performance. However, when Fc is appended to AlPorC(60), the expected improvement of the radical pair lifetime and the photovoltaic characteristics is not observed.

Sequential charge separation in two axially linked phenothiazine-aluminum(III) porphyrin-fullerene triads.

New supramolecular triads (PTZpy→AlPor-C(60), TPTZpy→AlPor-C(60)), containing aluminum(III) porphyrin (AlPor), fullerene (C(60)), and phenothiazine (phenothiazine = PTZ, 2-methylthiophenothaizine = TPTZ) have been constructed. In these triads the fullerene and phenothiazine units are bound axially to opposite faces of the porphyrin plane via covalent and coordination bonds, respectively. The ground- and excited-state properties of the triads and reference dyads are studied using steady-state and time-resolved spectroscopic techniques. The time-resolved data show that photoexcitation results in charge separation from the excited singlet state of the porphyrin to the C(60) unit, generating (Donor)py→AlPor(•+)-C(60)(•-), Donor = PTZ and TPTZ. A subsequent hole shift from the porphyrin to phenothiazine generates the charge-separated state (Donor)(•+)py→AlPor-C(60)(•-). The lifetime of the charge separation exhibits a modest increase from 39 ns in the absence of the donor to 100 ns in PTZpy→AlPor-C(60) and 83 ns in TPTZpy→AlPor-C(60). These lifetimes are discussed in terms of the electronic coupling between phenothiazine, the porphyrin, and C(60).

Spin−Spin Interactions in Porphyrin-Based Monoverdazyl Radical Hybrid Spin Systems

The spin-spin interactions in a complex consisting of a metalloporphyrin with a verdazyl radical attached at one of the beta positions of the porphyrin ring are investigated. The X-ray crystal structure of the copper porphyrin complex shows that the plane of the verdazyl moiety is oriented such that it is nearly perpendicular to the plane of the porphyrin ring so that weak magnetic interactions between the metal and radical are expected. Consistent with this expectation, magnetic susceptibility and continuous-wave electron paramagnetic resonance (EPR) measurements of the copper (d(9)) and vanadyl (d(1)) versions of the porphyrin show that the metal and radical are weakly antiferromagnetically coupled. Thus, the ground state is a singlet, but the triplet state is thermally accessible above approximately 5 K. Spin-polarized transient EPR measurements of the free-base analogue show that its lowest excited state is a quartet, indicating that the verdazyl radical couples ferromagnetically to the triplet excited state of the porphyrin. Low-temperature transient EPR measurements on the vanadyl porphyrin reveal that the lowest excited quintet state is populated. This implies that the antiferromagnetic coupling between the metal and radical observed in the ground state is switched to a ferromagnetic arrangement in the excited state by the presence of the unpaired electrons in the pi and pi* orbitals of the porphyrin.

Redox control of photoinduced electron transfer in axial terpyridoxy porphyrin complexes.

The photophysical properties of axial-bonding types (terpyridoxy)aluminum(III) porphyrin (Al(PTP)), bis(terpyridoxy)tin(IV) porphyrin (Sn(PTP) 2), and bis(terpyridoxy)phosphorus(V) porphyrin ([P(PTP) 2] (+)) are reported. Compared with their hydroxy analogues, the fluorescence quantum yields and singlet-state lifetimes were found to be lower for Sn(PTP) 2 and [P(PTP) 2] (+), whereas no difference was observed for Al(PTP). At low temperature, all of the compounds show spin-polarized transient electron paramagnetic resonance (TREPR) spectra that are assigned to the lowest excited triplet state of the porphyrin populated by intersystem crossing. In contrast, at room temperature, a triplet radical-pair spectrum that decays to the porphyrin triplet state with a lifetime of 175 ns is observed for [P(PTP) 2] (+), whereas no spin-polarized TREPR spectrum is found for Sn(PTP) 2 and only the porphyrin triplet populated by intersystem crossing is seen for Al(PTP). These results clarify the role of the internal molecular structure and the reduction potential for electron transfer from the terpyridine ligand to the excited porphyrin. It is argued that the efficiency of this process is dependent on the oxidation state of the metal/metalloid present in the porphyrin and the reorganization energy of the solvent.

Interfacial electron transfer in photoanodes based on phosphorus(V) porphyrin sensitizers co-deposited on SnO2 with the Ir(III)Cp* water oxidation precatalyst

We introduce phosphorus(V) porphyrins (PPors) as sensitizers of high-potential photoanodes with potentials in the 1.62–1.65 V (vs. NHE) range when codeposited with Ir(III)Cp* on SnO2. The ability of PPors to advance the oxidation state of the Ir(III)Cp* to Ir(IV)Cp*, as required for catalytic water oxidation, is demonstrated by combining electron paramagnetic resonance (EPR), steady-state fluorescence and time-resolved terahertz spectroscopy (TRTS) measurements, in conjunction with quantum dynamics simulations based on DFT structural models. Contrary to most other types of porphyrins previously analyzed in solar cells, our PPors bind to metal-oxide surfaces through axial coordination, a binding mode that makes them less prone to aggregation. The comparison of covalent binding via anchoring groups, such as m-hydroxidebenzoate (−OPh–COO−) and 3-(3-phenoxy)-acetylacetonate (−OPh–AcAc) as well as by direct deposition upon exchange of a chloride (Cl−) ligand provides insight on the effect of the anchoring group on forward and reverse light-induced interfacial electron transfer (IET). TRTS and quantum dynamics simulations reveal efficient photoinduced electron injection, from the PPor to the conduction band of SnO2, with faster and more efficient IET from directly bound PPor than from anchor-bound PPors. The photocurrents of solar cells, however, are higher for PPor–OPh–COO− and PPor–OPh–AcAc than for the directly bound PPor–O− for which charge recombination is faster. The high-potentials and the ability to induce redox state transitions of Ir(III)Cp* suggest that PPor/SnO2 assemblies are promising photoanode components for direct solar water-oxidation devices.

Modulation of Energy Transfer into Sequential Electron Transfer upon Axial Coordination of Tetrathiafulvalene in an Aluminum(III) Porphyrin–Free-Base Porphyrin Dyad

Axially assembled aluminum(III) porphyrin based dyads and triads have been constructed to investigate the factors that govern the energy and electron transfer processes in a perpendicular direction to the porphyrin plane. In the aluminum(III) porphyrin-free-base porphyrin (AlPor-Ph-H2Por) dyad, the AlPor occupies the basal plane, while the free-base porphyrin (H2Por) with electron withdrawing groups resides in the axial position through a benzoate spacer. The NMR, UV-visible absorption, and steady-state fluorescence studies confirm that the coordination of pyridine appended tetrathiafulvalene (TTF) derivative (TTF-py or TTF-Ph-py) to the dyad in noncoordinating solvents afford vertically arranged supramolecular self-assembled triads (TTF-py→AlPor-Ph-H2Por and TTF-Ph-py→AlPor-Ph-H2Por). Time-resolved studies revealed that the AlPor in dyad and triads undergoes photoinduced energy and/or electron transfer processes. Interestingly, the energy and electron donating/accepting nature of AlPor can be modulated by changing the solvent polarity or by stimulating a new competing process using a TTF molecule. In modest polar solvents (dichloromethane and o-dichlorobenzene), excitation of AlPor leads singlet-singlet energy transfer from the excited singlet state of AlPor ((1)AlPor*) to H2Por with a moderate rate constant (k(EnT)) of 1.78 × 10(8) s(-1). In contrast, excitation of AlPor in the triad results in ultrafast electron transfer from TTF to (1)AlPor* with a rate constant (k(ET)) of 8.33 × 10(9)-1.25 × 10(10) s(-1), which outcompetes the energy transfer from (1)AlPor* to H2Por and yields the primary radical pair TTF(+•)-AlPor(-•)-H2Por. A subsequent electron shift to H2Por generates a spatially well-separated TTF(+•)-AlPor-H2Por(-•) radical pair.

Light-induced hole transfer in a hypervalent phosphorus(V) octaethylporphyrin bearing an axially linked bis(ethylenedithio)tetrathiafulvalene

A phosphorus(V) porphyrin bearing an axially linked bis(ethylenedithio)tetrathiafulvalene, dyad 1, and its radical cation phosphorus(V) porphyrin-O-CH2-(bis(ethylenedithio)tetrathiafulvalene)+•, dyad 2, have been synthesized and studied as an electron hole donor-acceptor system. The absorption spectrum of dyad 1 does not show evidence for electronic coupling between the porphyrin and the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) moieties. However, the steady-state fluorescence of the porphyrin chromophore is quantitatively quenched and its transient fluorescence lifetime is shortened compared to a reference compound in which the BEDT-TTF moiety is replaced by a methoxy group. Chemical oxidation of the BEDT-TTF moiety in dyad 1 to give dyad 2 results in recovery of the fluorescence intensity. This behavior suggests that the fluorescence quenching in dyad 1 is the result of intramolecular hole transfer from the the excited porphyrin to the BEDT-TTF moiety. The occurence of hole transfer in dyad 1 is confirmed by freeze-trapping and time-resolved electron paramagnetic resonance (EPR) measurements. The freeze-trapping EPR experiments show that steady-state irradiation of the complex leads to accumulation of its radical cation (dyad 2) while the transient EPR measurements at 5 °C show that flash irradiation of dyad 1 results in formation of a radical-ion pair with a lifetime of at least 300 ns. The triplet state of the porphyrin, which is formed by intersystem crossing and gives a strong transient EPR spectrum in the reference compound, is not observed for dyad 1. Together, the fluorescence quenching and the polarization pattern of the radical pair suggest that the hole transfer occurs from the excited singlet state of the porphyrin with high efficiency.

Synthesis, spectroscopy and photochemistry of dyads and triads with porphyrins and bis(terpyridine)ruthenium(II) complex

A bis(terpyridine)ruthenium(II) complex ([Ru]2+) was covalently connected via a floppy -OCH2CH2O- spacer to the free-base porphyrin (H) or zinc(II) porphyrin (Zn) or both, to obtain dyads ([HRu]2+, [ZnRu]2+) and triads ([HRuH]2+, [ZnRuH]2+, [ZnRuZn]2+). These compounds have been fully characterized by MALDI, UV-vis, 1H NMR (1D and 1H-1H COSY) spectroscopies, and also by the cyclic and differential pulse voltammetric techniques. Absorption spectroscopy of these newly synthesized compounds shows that significant exciton coupling exists in non-polar solvents (cyclohexane and toluene) between the porphyrin ring and the bis(terpyridine)ruthenium(II) complex. Upon excitation within the Soret band of [HRu]2+/[HRuH]2+, free-base porphyrin fluorescence was found to be strongly quenched in non-polar and weakly quenched in polar solvents, probably due to ‘singlet-triplet’ energy transfer from the free-base porphyrin to the [Ru]2+ complex. Whereas, in [ZnRu]2+/[ZnRuZn]2+, zinc(II) porphyrin fluorescence was quantitatively and reasonably quenched in non-polar and polar solvents, respectively by mainly electron transfer from the zinc(II) porphyrin to the [Ru]2+ complex. The solvent plays a crucial role in the photophysical properties of these compounds, since the energy of the triplet metal-to-ligand charge-transfer (3MLCT) excited state is influenced by the polarity of the medium. Finally, [ZnRuH]2+ exhibits the combined fluorescence properties of [HRu]2+ and [ZnRu]2+ but the observed additional quenching in non-polar solvents for the zinc(II) porphyrin component is explained by energy transfer from the zinc(II) porphyrin to the free-base porphyrin and/or the bis(terpyridine)ruthenium(II) complex.

Factors Controlling the Redox Potential of ZnCe6 in an Engineered Bacterioferritin Photochemical 'Reaction Centre'

Photosystem II (PSII) of photosynthesis has the unique ability to photochemically oxidize water. Recently an engineered bacterioferritin photochemical ‘reaction centre’ (BFR-RC) using a zinc chlorin pigment (ZnCe6) in place of its native heme has been shown to photo-oxidize bound manganese ions through a tyrosine residue, thus mimicking two of the key reactions on the electron donor side of PSII. To understand the mechanism of tyrosine oxidation in BFR-RCs, and explore the possibility of water oxidation in such a system we have built an atomic-level model of the BFR-RC using ONIOM methodology. We studied the influence of axial ligands and carboxyl groups on the oxidation potential of ZnCe6 using DFT theory, and finally calculated the shift of the redox potential of ZnCe6 in the BFR-RC protein using the multi-conformational molecular mechanics–Poisson-Boltzmann approach. According to our calculations, the redox potential for the first oxidation of ZnCe6 in the BRF-RC protein is only 0.57 V, too low to oxidize tyrosine. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. We discuss the possibilities for modifying the BFR-RC to achieve this goal.

Nucleobase (A, T, G and C) appended tri-cationic water-soluble porphyrins: synthesis, characterization, binding and photocleavage studies with DNA

A series of nucleobase appended tri-cationic porphyrins (AT4, TT4, GT4 and CT4) have been synthesized and their binding and cleaving ability of DNA were investigated in this present study. UV-vis, fluorescence, circular dichroism and thermal melting studies were carried out to investigate binding of the porphyrin with calf thymus DNA (CTDNA). The apparent binding constant (Kapp) and the intrinsic binding constant (Kb) values calculated from UV-vis and fluorescence titrations, respectively, were comparable to 5,10,15,20-tetra(N-methylpyridinium-4-yl) porphyrin (H2T4) or slightly more for few compounds. Circular dichroism spectra of these porphyrins with DNA show variation in their mode of binding. Among the nucleobase appended tri-cationic porphyrins, the porphyrin in GT4 and TT4 exhibit strong intercalating ability in the DNA duplex whereas the porphyrin in AT4 and CT4 exhibit very less ability for intercalation. The intercalating efficiency of the porphyrin in GT4 is even stronger than that of the H2T4. The steric strain exists between the tri-cationic porphyrin moiety and the DNA may decrease depending on (a) the ease to exhibit keto-enol tautomerism due to the more acidic protons in guanine and thymine, (b) extended conjugation and (c) hydrogen bonding capability of the nucleobase moieties. Photocleavage proclivities with pBR322 DNA in the presence of light reveal that AT4, TT4 and CT4 show same amount of cleavage but GT4 shows more cleaving efficiency than H2T4 due to the stacked guanine moieties those are more reducing than a single guanine residue. The singlet oxygen mechanism that is responsible for the photocleavage was confirmed with various inhibitors and interestingly with Tiron (disodium salt of 1,2-dihydroxy-3,5-benzenedisulfonic acid) the photocleaving efficiency increases due to the inhibition of superoxide formation.