The ultrafast dynamics of 2′-deoxyguanosine 5′-monophosphate after excitation with ultraviolet light has been studied with femtosecond transient absorption (TA) and femtosecond stimulated Raman spectroscopy (FSRS). TA kinetics and transient anisotropy spectra reveal a rapid relaxation from the Franck–Condon region, producing an extremely red-shifted stimulated emission band at ∼440 nm that is formed after 200 fs and subsequent relaxation for 0.8–1.5 ps, consistent with prior studies. Viscosity dependence shows that the initial relaxation, before 0.5 ps, is the same in water or viscous glycerol/water mixtures, but after 0.5 ps the dynamics significantly slow down in a viscous solution. This indicates that large amplitude structural changes occur after 0.5 ps following photoexcitation. FSRS obtained with both 480 and 600 nm Raman pump pulses observe very broad Raman peaks at 509 and 1530 cm–1, as well as a narrower peak at 1179 cm–1. All of the Raman peaks decay with 0.7–1.3 ps time constants. The 1530 cm–1 peak also shows an increasing inhomogeneous linewidth over the first 0.3 ps. Our TA and FSRS data are consistent with a structurally inhomogeneous population in the S1 (La) state and, in particular, with previous theoretical models in which out-of-plane distortion at C2 and the amine move the molecule toward a conical intersection with the ground state. These FSRS data are the first to directly observe the structural inhomogeneity imparted upon the excited-state population by the broad, flat potential energy surface of the S1 (La) state.

Two new dyads have been synthesized and studied as photosensitizers for the light-driven generation of H2 from aqueous protons. One of the dyads, Dy-1, consists of a strongly absorbing Bodipy (dipyrromethene-BF2) dye and a platinum diimine benzenedithiolate (bdt) charge transfer (CT) chromophore, denoted as PtN2S2. The two components are connected through an amide linkage on the bdt side of the PtN2S2 complex. The second dyad, Dy-2, contains a diketopyrrolopyrrole dye that is linked directly to the acetylide ligands of a Pt diimine bis(arylacetylide) CT chromophore. The two dyads, as well as the Pt diimine bis(arylacetylide) CT chromophore, were attached to platinized TiO2 via phosphonate groups on the diimine through sonication of the corresponding esters, and each system was examined for photosensitizer effectiveness in photochemical generation of H2 from aqueous protons and electrons supplied by ascorbic acid. Of the three photosensitizers, Dy-1 is the most active under 530 nm radiation with an initial turnover frequency of 260 h–1 and a total of 6770 turnovers over 60 h of irradiation. When a “white” LED light source is used, samples with Dy-2 and the Pt diimine bis(arylacetylide) chromophore, while not as effective as Dy-1, perform relatively better. A key conclusion is that the presence of a strongly absorbing organic dye increases dyad photosensitizer effectiveness only if the energy of the CT excited state lies below that of the organic dye’s lowest excited state; if not, the organic dye does not improve the effectiveness of the CT chromophore for promoting electron transfer and the light-driven generation of H2. The nature of the spacer between the organic dye and the charge transfer chromophore also plays a role in the effectiveness of using dyads to improve light-driven energy-storing reactions.

A series of Boron-dipyrromethene (Bodipy) dyes were used as photosensitizers for photochemical hydrogen production in conjunction with [CoIII(dmgH)2pyCl] (where dmgH = dimethylglyoximate, py = pyridine) as the catalyst and triethanolamine (TEOA) as the sacrificial electron donor. The Bodipy dyes are fully characterized by electrochemistry, X-ray crystallography, quantum chemistry calculations, femtosecond transient absorption, and time-resolved fluorescence, as well as in long-term hydrogen production assays. Consistent with other recent reports, only systems containing halogenated chromophores were active for hydrogen production, as the long-lived triplet state is necessary for efficient bimolecular electron transfer. Here, it is shown that the photostability of the system improves with Bodipy dyes containing a mesityl group versus a phenyl group, which is attributed to increased electron donating character of the mesityl substituent. Unlike previous reports, the optimal ratio of chromophore to catalyst is established and shown to be 20:1, at which point this bimolecular dye/catalyst system performs 3–4 times better than similar chemically linked systems. We also show that the hydrogen production drops dramatically with excess catalyst concentration. The maximum turnover number of ∼700 (with respect to chromophore) is obtained under the following conditions: 1.0 × 10–4 M [Co(dmgH)2pyCl], 5.0 × 10–6 M Bodipy dye with iodine and mesityl substituents, 1:1 v:v (10% aqueous TEOA):MeCN (adjusted to pH 7), and irradiation by light with λ > 410 nm for 30 h. This system, containing discrete chromophore and catalyst, is more active than similar linked Bodipy–Co(dmg)2 dyads recently published, which, in conjunction with our other measurements, suggests that the nominal dyads actually function bimolecularly.

The first step of photosynthesis is the absorption of light by antenna complexes. Recent studies of light-harvesting complexes using two-dimensional electronic spectroscopy have revealed interesting coherent oscillations. Some contributions to those coherences are assigned to electronic coherence and therefore have implications for theories of energy transfer. To assign these femtosecond data and to gain insight into the interplay among electronic and vibrational resonances, we need detailed information on vibrations and coherences in the excited electronic state compared to the ground electronic state. Here, we used broad-band transient absorption and femtosecond stimulated Raman spectroscopies to record ground- and excited-state coherences in four related photosynthetic proteins: PC577 from Hemiselmis pacifica CCMP706, PC612 from Hemiselmis virescens CCAC 1635 B, PC630 from Chroomonas CCAC 1627 B (marine), and PC645 from Chroomonas mesostigmatica CCMP269. Two of those proteins (PC630 and PC645) have strong electronic coupling while the other two proteins (PC577 and PC612) have weak electronic coupling between the chromophores. We report vibrational spectra for the ground and excited electronic states of these complexes as well as an analysis of coherent oscillations observed in the broad-band transient absorption data.

A series of chalcogenorhodamine dyes with oxygen, sulfur, and selenium atoms in the xanthylium core was synthesized and used as chromophores for solar hydrogen production with a platinized TiO2 catalyst. Solutions containing the selenorhodamine dye generate more hydrogen [181 turnover numbers (TONs) with respect to chromophore] than its sulfur (30 TONs) and oxygen (20 TONs) counterparts. This differs from previous work incorporating these dyes into dye-sensitized solar cells (DSSCs), where the oxygen- and selenium-containing species perform similarly. Ultrafast transient absorption spectroscopy revealed an ultrafast electron transfer under conditions for dye-sensitized solar cells and a slower electron transfer under conditions for hydrogen production, making the chromophore’s triplet yield an important parameter. The selenium-containing species is the only dye for which triplet state population is significant, which explains its superior activity in hydrogen evolution. The discrepancy in rates of electron transfer appears to be caused by the presence or absence of aggregation in the system, altering the coupling between the dye and TiO2. This finding demonstrates the importance of understanding the differences between, as well as the effects of the conditions for DSSCs and solar hydrogen production.

The effects of solvent and substituents on a multichromophoric complex containing a boron-dipyrromethene (Bodipy) chromophore and Pt(bpy)(bdt) (bpy = 2,2′-bipyridine, bdt =1,2-benzenedithiolate) were studied using steady-state absorption, emission, and ultrafast transient absorption spectroscopy. When the Bodipy molecule is connected to either the bpy or bdt in acetonitrile, excitation ultimately leads to the dyad undergoing triplet energy transfer (TEnT) from the redox-active Pt triplet mixed−metal-ligand−to−ligand′ charge transfer (3MMLL′CT) state to the Bodipy 3ππ* state in 8 and 160 ps, respectively. This is disadvantageous for solar energy applications. Here, we investigate two methods to lower the energy of the 3MMLL′CT state, thereby making TEnT unfavorable. By switching to a low dielectric constant solvent, we are able to extend the lifetime of the 3MMLL′CT state to over 1 ns, the time frame of our experiment. Additionally, electron-withdrawing groups, such as carboxylate and phosphonate esters, on the bpy lower the energy of the 3MMLL′CT state such that the photoexcited dyad remains in that state and avoids TEnT to the Bodipy 3ππ* state. It is also shown that a single methylene spacer between the bpy and phosphonate ester is sufficient to eliminate this effect, raising the energy of the 3MMLL′CT state and inducing relaxation to the 3ππ*.

We present theoretical and experimental data for the attenuation of the cascade signal in two-dimensional femtosecond stimulated Raman spectroscopy (2D-FSRS). In previous studies, the cascade signal, caused by two third-order interactions, was found to overwhelm the desired fifth-order signal that would measure vibrational anharmonic coupling. Theoretically, it is found that changing the phase-matching conditions and sample concentration would attenuate the cascade signal, while only slightly decreasing the fifth-order signal. By increasing the crossing angle between the Raman pump and probe and the impulsive pump and probe, the phase-matching efficiency of the cascade signal is significantly attenuated, while the fifth-order efficiency remains constant. The dilution experiments take advantage of the difference in the concentration dependence for the fifth-order and cascade signal, in which the fifth-order signal is proportional to concentration and the cascade signal is proportional to concentration squared. Experimentally, it is difficult to see a trend in the data due to instability in signal in the phase-matching experiments and lack of signal at low concentrations in the dilution experiments.

4-(Dimethylamino)benzonitrile (DMABN) has been one of the most studied photoinduced charge-transfer (CT) compounds for over 50 years, but due to the complexity of its excited electronic states and the importance of both intramolecular and solvent reorganization, the detailed microscopic mechanism of the CT is still debated. In this work, we have probed the ultrafast intramolecular CT process of DMABN in methanol using broad-band transient absorption spectroscopy from 280 to 620 nm and ultraviolet femtosecond stimulated Raman spectroscopy (FSRS) incorporating a 330 nm Raman pump pulse. Global analysis of the transient absorption kinetics revealed dynamics occurring with three distinct time constants: relaxation from the Franck–Condon La state to the lower locally excited (LE) Lb state in 0.3 ps, internal conversion in 2–2.4 ps that produces a vibrationally hot CT state, and vibrational relaxation within the CT state occurring in 6 ps. The 330 nm FSRS spectra established the dynamics along three vibrational coordinates: the ring-breathing stretch, νph, at 764 cm–1 in the CT state; the quinoidal C═C stretch, νCC, at 1582 cm–1 in the CT state; and the nitrile stretch, νCN, at 2096 cm–1 in the CT state. FSRS spectra collected with a 400 nm Raman pump probed the dynamics of the 1174 cm–1 CH bending vibration, δCH. Spectral shifts of each of these modes occur on the 2–20 ps time scale and were analyzed in terms of the vibrational anharmonicity of the CT state, calculated using density functional theory. The frequencies of the δCH and νCC modes upshift with a 6–7 ps time constant, consistent with their off-diagonal anharmonic coupling to other modes that act as receiving modes during the CT process and then cool in 6–7 ps. It was found that the spectral down-shifts of the δCH and νCN modes are inconsistent with vibrational anharmonicity and are instead due to changes in molecular structure and hydrogen bonding that occur as the molecule relaxes within the CT state potential energy surface.

A series of halogenated boron-dipyrromethene (Bodipy) chromophores with potential applications in solar energy conversion were synthesized and characterized by steady state and ultrafast laser spectroscopy. The ultrafast dynamics of the chromophores were compared between a series containing H, Br, or I at the 2,6 positions of the Bodipy dye. The parent Bodipy has a fluorescent lifetime (τfl) of 3−5 ns, a fluorescence quantum yield (Φfl) of 0.56, and negligible triplet state yield. Bromination enhances the intersystem crossing (ISC) such that τfl and Φfl decrease to ∼1.2 ns and 0.11, respectively, while iodination further accelerates ISC so that τfl is only ∼130 ps and Φfl is 0.011. Transient absorption experiments lead to the observation of excited state absorption bands from the singlet (S1) and triplet (T1) states at ∼345 and 447 nm, respectively, and characterization of ISC via the dynamics of these bands and the decay of S1 stimulated emission.Keywords (keywords): femtosecond transient absorption; sensitizers; solar energy; triplet; ultrafast;

This work presents a theoretical treatment of the vibrational line shape generated in a femtosecond stimulated Raman spectroscopy (FSRS) experiment under conditions in which the probed vibration undergoes a significant frequency shift during its free induction decay. This theory is applied to simulate the FSRS lineshapes previously observed in rhodopsin (Kukura et al. Science2005, 310, 1006). The previously determined relaxation times for formation of the trans-photoproduct of rhodopsin were calculated using an incorrect equation for the time dependence of the observed frequency shifts. Here the data are reanalyzed by calculation of the corrected frequency sweep occurring during the vibrational free induction decay. It is shown that the calculated frequency shifts and general conclusions of the original work are sound but that the coherent vibrational frequency shifts of the C10, C11, and C12 hydrogen-out-of-plane vibrations occur with a 140 fs time constant rather than the previously reported 325 fs time constant. This time constant provides an important constraint for models of the dynamics of the cis to trans isomerization process.

The dyads 3, 4, and 6, combining the Bodipy chromophore with a Pt(bpy)(bdt) (bpy = 2,2′-bipyridine, bdt = 1,2-benzenedithiolate, 3 and 6) or a Pt(bpy)(mnt) (mnt = maleonitriledithiolate, 4) moiety, have been synthesized and studied by UV−vis steady-state absorption, transient absorption, and emission spectroscopies and cyclic voltammetry. Comparison of the absorption spectra and cyclic voltammograms of dyads 3, 4, and 6 and those of their model compounds 1a, 2, 5, and 7 shows that the spectroscopic and electrochemical properties of the dyads are essentially the sum of their constituent chromophores, indicating negligible interaction of the constituent chromophores in the ground state. However, emission studies on 3 and 6 show a complete absence of both Bodipy-based fluorescence and the characteristic luminescence of the Pt(bpy)(bdt) unit. Dyad 4 shows a weak Pt(mnt)-based emission. Transient absorption studies show that excitation of the dyads into the Bodipy-based 1ππ* excited state is followed by singlet energy transfer (SEnT) to the Pt(dithiolate)-based 1MMLL′CT (mixed metal-ligand to ligand charge transfer) excited state ( = 0.6 ps, = 0.5 ps, and = 1.6 ps), which undergoes rapid intersystem crossing to the 3MMLL′CT state due to the heavy Pt(II) ion. The 3MMLL′CT state is then depopulated by triplet energy transfer (TEnT) to the low-lying Bodipy-based 3ππ* excited state ( = 8.2 ps, = 5 ps, and = 160 ps). The transition assignments are supported by TD-DFT calculations. Both energy-transfer processes are shown to proceed via a Dexter electron exchange mechanism. The much longer time constants for dyad 6 relative to 3 are attributed to the significantly poorer coupling and resonance of charge-separated species that are intermediates in the electron exchange process.

Femtosecond stimulated Raman spectroscopy (FSRS) and femtosecond transient absorption have been used to probe the photoinduced charge transfer (CT) dynamics of 4-(dimethylamino)benzonitrile in methanol and n-hexane. Through a combined analysis of temporal changes in the Raman modes and transient absorption kinetics, a more complete picture of the reaction coordinate of the intramolecular charge transfer process has been established. FSRS spectra of the phenyl C═C stretching mode (Wilson mode 8a) at 1607 cm−1, which shifts to 1581 cm−1 in the CT state, and transient absorption measurements ranging from 360 to 700 nm support internal conversion from the locally excited to the charge transfer state in 4−5 ps and then a subsequent vibrational relaxation within the CT state manifold on a 6−8 ps time scale. Dramatic shifting and narrowing of the 1581 cm−1 quinoidal C═C stretch (ν8a) on the ∼7 ps time scale indicates that the quinoidal distortion is an important probe of the CT reaction dynamics. The cause of the spectral shifts is determined by comparing the observed shifts in the vibrational spectrum to anharmonic couplings computed for the benzonitrile radical anion by density functional theory (DFT) and with quantitative theoretical models of the solvent induced vibrational peak shifts. The DFT calculations indicate that the 10 cm−1 downshift of the C═C stretch is most likely attributable to significant vibrational excitation in nontotally symmetric modes that are strongly anharmonically coupled to the C═C stretch.