Chemically regulating Rh(I)-Bodipy photoredox switches.

The ability of Rh(I) centers to undergo photoinduced electron transfer from discrete metal orbitals to Bodipy fluorophores is mediated through reversible coordination chemistry.

Conformational gating of long distance electron transfer through wire-like bridges in donor-bridge-acceptor molecules.

A series of five donor-bridge-acceptor (DBA) molecules in which the donor is tetracene, the acceptor is pyromellitimide, and the bridge molecules are oligo-p-phenylenevinylenes (OPV) of increasing length has been shown to undergo electron transfer (ET) by means of two mechanisms. When the bridge is short, strongly distance dependent superexchange dynamics dominates, whereas when the bridge is longer, bridge-assisted hopping dynamics prevails. The latter mechanism results in relatively soft distance dependence for ET in which the OPV oligomers act effectively as molecular wires. We now report studies on the critical influence that bridge dynamics have on electron transfer through these oligomers. The temperature dependence of the charge separation (CS) rates in all five molecules does not appear to obey the predictions of standard ET theories based upon the Condon approximation. All five molecules show behavior consistent with CS being "gated" by torsional motion between the tetracene donor and the first bridge phenyl ring. This is based on the near equivalence of the CS activation energies measured for all five molecules with the frequency of a known vibrational mode in 5-phenyltetracene. In the molecule containing a trans-stilbene bridge, a competition occurs between the tetracene-phenyl torsional motion and one that occurs between the vinyl group and the phenyls linked to it. This results in complex temperature-dependent CS that exhibits both activated and negatively activated regimes. The charge recombination (CR) reactions within the molecules which have the two shortest bridges, namely phenyl and trans-stilbene, show a weaker dependence on these molecular motions. The three molecules with the longest bridges all display complex temperature dependencies in both their rates of CS and CR, most likely because of the complex torsional motions, which arise from the multiple phenyl-vinyl linkages. The data show that long-distance electron transfer and therefore wire-like behavior within conjugated bridge molecules depend critically on these low-frequency torsional motions. Molecular device designs that utilize such bridges will need to address these issues.

Photophysics of pi-conjugated metal-organic oligomers: aryleneethynylenes that contain the (bpy)Re(CO)(3)Cl chromophore.

A comprehensive study of a series of four monodisperse, metal-organic pi-conjugated oligomers of varying length is reported. The oligomers are based on the aryleneethynylene architecture, and they contain a 2,2'-bipyridine-5,5'-diyl (bpy) metal binding unit. The photophysical properties of the free oligomers and their complexes with the (L)Re(I)(CO)(3)X chromophore (where L = the bpy-oligomer and X = Cl or NCCH(3)) were explored by a variety of methods including electrochemistry, UV-visible absorption, variable temperature photoluminescence (PL), transient absorption (TA), and time-resolved electron paramagnetic spectroscopy (TREPR). The absorption of the free oligomers and the metal complexes is dominated by the pi,pi* transitions of the pi-conjugated oligomers. The free oligomers feature a strong blue fluorescence that is quenched entirely in the (L)Re(I)(CO)(3)X complexes. The metal-oligomers feature a weak, relatively long-lived red photoluminescence that is assigned to emission from both the (3)pi,pi* manifold of the pi-conjugated system and the dpi Re --> pi* bpy-oligomer metal-to-ligand charge transfer ((3)MLCT) state. On the basis of a detailed analysis of the PL, TA, and TREPR results an excited-state model is developed which indicates that the oligomer-based (3)pi,pi* state and the (3)MLCT states are in close energetic proximity. Consequently the photophysical properties reflect a composite of the properties of the two excited-state manifolds.

Dynamics of photoinduced charge transfer and hole transport in synthetic DNA hairpins.

The dynamics of photoinduced charge separation and charge recombination processes in synthetic DNA hairpins have been investigated by means of femtosecond transient absorption spectroscopy. The driving force and distance dependence of charge-transfer processes involving singlet acceptors and nucleobase donors are consistent with a single-step superexchange mechanism in which the electronic coupling between the donor and acceptor is strongly distance dependent. The dynamics of reversible hole transport between a primary guanine donor and nearby GG or GGG sequences has also been determined and establishes that these sequences are very shallow hole traps.

Direct measurement of hole transport dynamics in DNA.

Our understanding of oxidative damage to double helical DNA and the design of DNA-based devices for molecular electronics is crucially dependent upon elucidation of the mechanism and dynamics of electron and hole transport in DNA. Electrons and holes can migrate from the locus of formation to trap sites, and such migration can occur through either a single-step "superexchange" mechanism or a multistep charge transport "hopping" mechanism. The rates of single-step charge separation and charge recombination processes are found to decrease rapidly with increasing transfer distances, whereas multistep hole transport processes are only weakly distance dependent. However, the dynamics of hole transport has not yet been directly determined. Here we report spectroscopic measurements of photoinduced electron transfer in synthetic DNA that yield rate constants of approximately 5 x 10(7) s(-1) and 5 x 10(6) s(-1), respectively, for the forward and return hole transport from a single guanine base to a double guanine base step across a single adenine. These rates are faster than processes leading to strand cleavage, such as the reaction of guanine cation radical with water, thus permitting holes to migrate over long distances in DNA. However, they are too slow to compete with charge recombination in contact ion pairs, a process which protects DNA from photochemical damage.

Distance-dependent electron transfer in DNA hairpins.

The distance dependence of photoinduced electron transfer in duplex DNA was determined for a family of synthetic DNA hairpins in which a stilbene dicarboxamide forms a bridge connecting two oligonucleotide arms. Investigation of the fluorescence and transient absorption spectra of these hairpins established that no photoinduced electron transfer occurs for a hairpin that has six deoxyadenosine-deoxythymidine base pairs. However, the introduction of a single deoxyguanosine-deoxycytidine base pair resulted in distance-dependent fluorescence quenching and the formation of the stilbene anion radical. Kinetic analysis suggests that duplex DNA is somewhat more effective than proteins as a medium for electron transfer but that it does not function as a molecular wire.

Antenna excited state decay kinetics establish primary electron transfer in reaction centers as heterogeneous.

The decay of the excited primary electron donor P* in bacterial photosynthetic reaction centers (both membrane-bound and detergent-isolated) has been observed to be nonexponential on a time scale of some tens of picoseconds. Although the multipicosecond nonexponentiality of P* has been ascribed to heterogeneity in teh rate of primary electron transfer (PET), the decay kinetics can be interpreted equally well using homogeneous models. To address this ambiguity, we studied the decay of excited bacteriochlorophyll (Bchl) in the membrane-bound core antenna/reaction center complexes of wild-type and mutant reaction center strains of Rhodobacter capsulatus. Reaction centers isolated from these same strains display a range of multiexponentiality in primary charge separation. The mutant strains carry substitutions of amino acids residing near the monomeric Bchl on the active and/or inactive sides of the reaction center. Transient absorption measurements monitoring the Qy bleach of antenna Bchls require at least two exponential components to fit all decays. The wild type was fitted with equal-amplitude components whose lifetimes are 24 and 65 ps. The shortest-lived component is relatively insensitive to mutation, in contrast to the longer-lived component(s) whose amplitude and magnitude were dramatically perturbed by amino acid substitutions. Unlike the situation with isolated reaction centers, here the only kinetic models consistent with the data are those in which the primary electron-transfer rate constant is heterogeneous, suggesting at least two structural populations of RCs. PET in the population with the shortest-lived antenna decay causes the kinetics to be transfer-to-trap-limited, whereas the kinetics in the other population(s)--having longer-lived antenna decays--are limited by the rate of PET. Observation of both types of kinetic limitation within a single light-harvesting system is unexpected and complicates any discussion of the rate-limiting step of light energy utilization in photosynthesis.

The lifetimes and energies of the first excited singlet states of diadinoxanthin and diatoxanthin: the role of these molecules in excess energy dissipation in algae.

The lifetimes of the first excited singlet states (2(1)A(g)) of diadinoxanthin and diatoxanthin, carotenoids involved in the xanthophyll cycle in some genera of algae, have been measured by femtosecond time-resolved optical spectroscopy to be 22.8 +/- 0.1 ps and 13.3 +/- 0.1 ps, respectively. Using the energy gap law for radiationless transitions set forth by Englman and Jortner (Mol. Phys. 18 (1970) 145-164), these lifetimes correspond to S1 excited state energies of 15210 cm-1 for diadinoxanthin and 14620 cm-1 for diatoxanthin. The lowest excited singlet state energy of Chl a has an energy of 14700 cm-1. The fact that the S1 state energy of diadinoxanthin lies above that of Chl a, whereas the S1 state energy of diatoxanthin lies below that of Chl a, suggests that the xanthophyll cycle involving the enzymatic interconversion of diadinoxanthin and diatoxanthin may play a role in regulating energy flow between these molecules and Chl a in many species of algae, essentially fulfilling a role identical to that proposed for violaxanthin and zeaxanthin in higher plants and green algae (Frank et al. (1994) Photosyn. Res. 41, 389-395).

Excitation energy transfer and charge separation in the isolated Photosystem II reaction center.

The nature of excitation energy transfer and charge separation in isolated Photosystem II reaction centers is an area of considerable interest and controversy. Excitation energy transfer from accessory chlorophyll a to the primary electron donor P680 takes place in tens of picoseconds, although there is some evidence that thermal equilibration of the excitation between P680 and a subset of the accessory chlorophyll a occurs on a 100-fs timescale. The intrinsic rate for charge separation at low temperature is accepted to be ca. (2 ps)(-1), and is based on several measurements using different experimental techniques. This rate is in good agreement with estimates based on larger sized particles, and is similar to the rate observed with bacterial reaction centers. However, near room temperature there is considerable disagreement as to the observed rate for charge separation, with several experiments pointing to a ca. (3 ps)(-1) rate, and others to a ca. (20 ps)(-1) rate. These processes and the experiments used to measure them will be reviewed.

Near-transform-limited visible and near-IR femtosecond pulses from optical parametric amplification using Type II beta-barium borate.

Type II phase-matched beta-barium borate is used in the f irst stage of amplif ication of a white-light continuum in a two-stage optical parametric amplifier pumped by the second harmonic of a regeneratively amplified Ti:sapphire laser system operating at 824 nm. Near-transform-limited sub-190-fs pulses with microjoule energies are achieved in the signal branch, which is tunable from 475 nm to degeneracy. This system effectively bridges the wavelength gap between the fundamental and the second harmonic of amplified Ti:sapphire laser systems.

Optical parametric amplification of femtosecond pulses tunable from the blue to the infrared with microjoule energies.

A white-light continuum is used to seed a two-stage optical parametric amplifier pumped by the second harmonic of a regeneratively amplified Ti:sapphire laser system operating at 824 nm. Microjoule energies are achieved in the signal branch, which is tunable from 472 to 785 nm. Near-transform-limited sub-200-fs pulses are attainable over the vast majority of the tuning range.

Femtosecond photodichroism studies of isolated photosystem II reaction centers.

Photosynthetic conversion of light energy into chemical potential begins in reaction center protein complexes, where rapid charge separation occurs with nearly unit quantum efficiency. Primary charge separation was studied in isolated photosystem II reaction centers from spinach containing 6 chlorophyll a, 2 pheophytin a (Pheo), 1 cytochrome b559, and 2 beta-carotene molecules. Time-resolved pump-probe kinetic spectroscopy was carried out with 105-fs time resolution and with the pump laser polarized parallel, perpendicular, and at the magic angle (54.7 degrees) relative to the polarized probe beam. The time evolution of the transient absorption changes due to the formation of the oxidized primary electron donor P680+ and the reduced primary electron acceptor Pheo- were measured at 820 nm and 545 nm, respectively. In addition, kinetics were obtained at 680 nm, the wavelength ascribed to the Qy transition of the primary electron donor P680 in the reaction center. At each measured probe wavelength the kinetics of the transient absorption changes can be fit to two major kinetic components. The relative amplitudes of these components are strongly dependent on the polarization of the pump beam relative to that of the probe. At the magic angle, where no photoselection occurs, the amplitude of the 3-ps component, which is indicative of the charge separation, dominates. When the primary electron acceptor Pheo is reduced prior to P680 excitation, the 3-ps component is eliminated.

Photophysics of the carotenoids associated with the xanthophyll cycle in photosynthesis.

Green plants use the xanthophyll cycle to regulate the flow of energy to chlorophylla within photosynthetic proteins. Under conditions of low light intensity violaxanthin, a carotenoid possessing nine conjugated double bonds, functions as an antenna pigment by transferring energy from its lowest excited singlet state to that of chlorophylla within light-harvesting proteins. When the light intensity increases, violaxanthin is biochemically transformed into zeaxanthin, a carotenoid that possesses eleven conjugated double bonds. The results presented here show that extension of the [Symbol: see text] conjugation of the polyene lowers the energy of the lowest excited singlet state of the carotenoid below that of chlorophylla. As a consequence zeaxanthin can act as a trap for the excess excitation energy on chlorophylla pigments within the protein, thus regulating the flow of energy within photosynthetic light-harvesting proteins.

Picosecond optical switching based on biphotonic excitation of an electron donor-acceptor-donor molecule.

An electron donor-acceptor-donor molecule consisting of two porphyrin donors rigidly attached to the two-electron acceptor N,N'-diphenyl-3,4,9,10-perylenebis(dicarboximide) acts as a light intensity-dependent molecular switch on a picosecond time scale. Excitation of the porphyrins within this molecule with subpicosecond laser pulses results in single or double reduction of the acceptor depending on the light intensity. The singly and doubly reduced electron acceptors absorb light strongly at 713 and 546 nanometers, respectively. Because these absorption changes are produced solely by electron transfers, this molecular switch effectively has no moving parts and switches significantly faster than photochromic molecules that must undergo changes in molecular structure.

Determination of the primary charge separation rate in isolated photosystem II reaction centers with 500-fs time resolution.

We have measured directly the rate of formation of the oxidized chlorophyll a electron donor (P680(+)) and the reduced electron acceptor pheophytin a(-) (Pheoa(-)) following excitation of isolated spinach photosystem II reaction centers at 4 degrees C. The reaction-center complex consists of D(1), D(2), and cytochrome b-559 proteins and was prepared by a procedure that stabilizes the protein complex. Transient absorption difference spectra were measured from 440 to 850 nm as a function of time with 500-fs resolution following 610-nm laser excitation. The formation of P680(+)-Pheoa(-) is indicated by the appearance of a band due to P680(+) at 820 nm and corresponding absorbance changes at 505 and 540 nm due to formation of Pheoa(-). The appearance of the 820-nm band is monoexponential with tau = 3.0 +/- 0.6 ps. The time constant for decay of (1*)P680, the lowest excited singlet state of P680, monitored at 650 nm, is tau = 2.6 +/- 0.6 ps and agrees with that of the appearance of P680(+) within experimental error. Treatment of the photosystem II reaction centers with sodium dithionite and methyl viologen followed by exposure to laser excitation, conditions known to result in accumulation of Pheoa(-), results in formation of a transient absorption spectrum due to (1*)P680. We find no evidence for an electron acceptor that precedes the formation of Pheoa(-).

Measurement of the extent of electron transfer to the bacteriopheophytin in the M-subunit in reaction centers of Rhodopseudomonas viridis.

We have measured the extent of flash-induced electron transfer from the bacteriochlorophyll dimer, P, to the bacteriopheophytin in the M-subunit, HM, in reaction centers of Rhodopseudomonas viridis. This has been done by measuring the transient states produced by excitation of reaction centers trapped in the PHL (-)HM state at 90 K. Under these conditions the normal forward electron transfer to the bacteriopheophytin in the L-subunit, HL, is blocked and the yield of transient P(+)HM (-) can be estimated with respect to the lifetime of P(*). Under these conditions flash induced absorbance decreases of the bacteriochlorophyll dimer 990 nm band suggest that a transient P(+) state is formed with a quantum yield of 0.09±0.06 compared to that formed during normal photochemistry. These transient measurements provide an upper limited on the yield of a transient P(+) HM (-) state. An estimate of 0.09 as the yield of the P(+) HM (-) state is consistent with all current observations. This estimate and the lifetime of P(*) suggest that the electron transfer rate from P(*) to HM, kM, is about 5 × 10(9) sec(-1) (τM = 200ps). These measurements suggest that the a branching ratio kL/kM is on the order of 200. The large value of the branching ratio is remarkable in view of the structural symmetry of the reaction center. This measurement should be useful for electron transfer calculations based upon the reaction center structure.

Determination of the primary charge separation rate in Photosystem II reaction centers at 15 K.

We have measured the rate constant for the formation of the oxidized chlorophyll a electron donor (P680(+)) and the reduced electron acceptor pheophytin a (-) (Pheo a (-)) following excitation of isolated Photosystem II reaction centers (PS II RC) at 15 K. This PS II RC complex consists of D1, D2, and cytochrome b-559 proteins and was prepared by a procedure which stabilizes the protein complex. Transient absorption difference spectra were measured from 450-840 nm as a function of time with 500fs resolution following 610 nm laser excitation. The formation of P680(+)-Pheo a (-) is indicated by the appearance of a band due to P680(+) at 820 nm and corresponding absorbance changes at 490, 515 and 546 nm due to the formation of Pheo a (-). The appearance of the 490 nm and 820 nm bands is monoexponenital with τ=1.4±0.2 ps. Treatment of the PS II RC with sodium dithionite and methyl viologen followed by exposure to laser excitation results in accumulation of Pheo a (-). Laser excitation of these prereduced RCs at 15 K results in formation of a transient absorption spectrum assigned to (1*)P680. We observe wavelength-dependent kinetics for the recovery of the transient bleach of the Qy absorption bands of the pigments in both untreated and pre-reduced PS II RCs at 15K. This result is attributed to an energy transfer process within the PS II RC at low temperature that is not connected with charge separation.

The rate of formation of P700(+)-A 0 (-) in photosystem I particles from spinach as measured by picosecond transient absorption spectroscopy.

Photosystem I particles containing 30-40 chlorophyll a molecules per primary electron donor P700 were subjected to 1.5 ps low density laser flashes at 610 nm resulting in excitation of the antenna chlorophyll a molecules followed by energy transfer to P700 and subsequent oxidation of P700. Absorbance changes were monitored as a function of time with 1.5 ps time resolution. P700 bleaching (decrease in absorbance) occurred within the time resolution of the experiment. This is attributed to the formation of (1)P700.(*) This observation was confirmed by monitoring the rise of a broad absorption band near 810 nm due to chlorophyll a excited singlet state formation. The appearance of the initial bleach at 700 nm was followed by a strong bleaching at 690 nm. The time constant for the appearance of the 690 nm bleach is 13.7±0.8 ps. In the near-infrared region of the spectrum, the 810 nm band (which formed upon the excitation of the photosystem I particles) diminished to about 60% of its original intensity with the same 13.7 ps time constant as the formation of the 690 nm band. The spectral changes are interpreted as due to the formation of the charge separated state P700(+)-A0 (-), where A0 is the primary electron acceptor chlorophyll a molecule.