Justin P. Lomont

X‐ray Transient Absorption and Picosecond IR Spectroscopy of Fulvalene(tetracarbonyl)diruthenium on Photoexcitation

Caught in the light: The fulvalene diruthenium complex shown on the left side of the picture captures sun light, causing initial Ru-Ru bond rupture to furnish a long-lived triplet biradical of syn configuration. This species requires thermal activation to reach a crossing point (middle) into the singlet manifold on route to its thermal storage isomer on the right through the anti biradical.

Study of Heat Transfer Dynamics from Gold Nanorods to the Environment via Time-Resolved Infrared Spectroscopy.

Studying the local solvent surrounding nanoparticles is important to understanding the energy exchange dynamics between the particles and their environment, and there is a need for spectroscopic methods that can dynamically probe the solvent region that is in nearby contact with the nanoparticles. In this work, we demonstrate the use of time-resolved infrared spectroscopy to track changes in a vibrational mode of local water on the time scale of hundreds of picoseconds, revealing the dynamics of heat transfer from gold nanorods to the local water environment. We applied this probe to a prototypical plasmonic photothermal system consisting of organic CTAB bilayer capped gold nanorods, as well as gold nanorods coated with varying thicknesses of inorganic mesoporous-silica. The heat transfer time constant of CTAB capped gold nanorods is about 350 ps and becomes faster with higher laser excitation power, eventually generating bubbles due to superheating in the local solvent. Silica coating of the nanorods slows down the heat transfer and suppresses the formation of superheated bubbles.

Ultrafast Infrared Studies of the Role of Spin States in Organometallic Reaction Dynamics

The importance of spin state changes in organometallic reactions is a topic of significant interest, as an increasing number of reaction mechanisms involving changes of spin state are consistently being uncovered. The potential influence of spin state changes on reaction rates can be difficult to predict, and thus this class of reactions remains among the least well understood in organometallic chemistry. Ultrafast time-resolved infrared (TRIR) spectroscopy provides a powerful tool for probing the dynamics of spin state changes in organometallic catalysis, as such processes often occur on the picosecond to nanosecond time scale and can readily be monitored in the infrared via the absorptions of carbonyl reporter ligands. In this Account, we summarize recent work from our group directed toward identifying trends in reactivity that can be used to offer predictive insight into the dynamics of coordinatively unsaturated organometallic reaction intermediates. In general, coordinatively unsaturated 16-electron (16e) singlets are able to coordinate to solvent molecules as token ligands to partially stabilize the coordinatively unsaturated metal center, whereas 16e triplets and 17-electron (17e) doublets are not, allowing them to diffuse more rapidly through solution than their singlet counterparts. Triplet complexes typically (but not always) undergo spin crossover prior to solvent coordination, whereas 17e doublets do not coordinate solvent molecules as token ligands and cannot relax to a lower spin state to do so. 16e triplets are typically able to undergo facile spin crossover to yield a 16e singlet where an associative, exothermic reaction pathway exists. The combination of facile spin crossover with faster diffusion through solution for triplets can actually lead to faster catalytic reactivity than for singlets, despite the forbidden nature of these reactions. We summarize studies on odd-electron complexes in which 17e doublets were found to display varying behavior with regard to their tendency to react with 2-electron donor ligands to form 19-electron (19e) adducts. The ability of 19e adducts to serve as reducing agents in disproportionation reactions depends on whether the excess electron density localized at the metal center or at a ligand site. The reactivity of both 16e and 17e complexes toward a widely used organic nitroxyl radical (TEMPO) are reviewed, and both classes of complexes generally react similarly via an associative mechanism with a low barrier to these reactions. We also describe recent work targeted at unraveling the photoisomerization mechanism of a thermal-solar energy storage complex in which spin state changes were found to play a crucial role. Although a key triplet intermediate was found to be required for this photoisomerization mechanism to proceed, the details of why this triplet is formed in some complexes (those based on ruthenium) and not others (those based on iron, molybdenum, or tungsten) remains uncertain, and further exploration in this area may lead to a better understanding of the factors that influence intramolecular and excited state spin state changes.

Ultrafast observation of a solvent dependent spin state equilibrium in CpCo(CO).

We report the observation of a solvent-dependent spin state equilibrium in the 16-electron photoproduct CpCo(CO). Time-resolved infrared spectroscopy has been used to observe the concurrent formation of two distinct solvated monocarbonyl photoproducts, both of which arise from the same triplet CpCo(CO) precursor. Experiments in different solvent environments, combined with electronic structure theory calculations, allow us to assign the two solvated photoproducts to singlet and triplet CpCo(CO)(solvent) complexes. These results add to our previous picture of triplet reactivity for 16-electron organometallic photoproducts, in which triplets were not believed to interact strongly with solvent molecules. In the case of this photoproduct, it appears that spin crossover does not present a significant barrier to reactivity, and relative thermodynamic stabilities determine the spin state of the CpCo(CO) photoproduct in solution on the picosecond time scale. While the existence of transition metal complexes with two thermally accessible spin states is well-known, this is, to our knowledge, the first observation of a transient photoproduct that exhibits an equilibrium between two stable spin states, and also the first observed case in which a solvent has been able to coordinate as a token ligand to two spin states of the same photoproduct.

Reactivity of TEMPO toward 16- and 17-electron organometallic reaction intermediates: a time-resolved IR study.

The (2,2,6,6-tetramethylpiperidin-1-yl)oxyl radical (TEMPO) has been employed for an extensive range of chemical applications, ranging from organometallic catalysis to serving as a structural probe in biological systems. As a ligand in an organometallic complex, TEMPO can exhibit several distinct coordination modes. Here we use ultrafast time-resolved infrared spectroscopy to study the reactivity of TEMPO toward coordinatively unsaturated 16- and 17-electron organometallic reaction intermediates. TEMPO coordinates to the metal centers of the 16-electron species CpCo(CO) and Fe(CO)4, and to the 17-electron species CpFe(CO)2 and Mn(CO)5, via an associative mechanism with concomitant oxidation of the metal center. In these adducts, TEMPO thus behaves as an anionic ligand, characterized by a pyramidal geometry about the nitrogen center. Density functional theory calculations are used to facilitate interpretation of the spectra and to further explore the structures of the TEMPO adducts. To our knowledge, this study represents the first direct characterization of the mechanism of the reaction of TEMPO with coordinatively unsaturated organometallic complexes, providing valuable insight into its reactions with commonly encountered reaction intermediates. The similar reactivity of TEMPO toward each of the species studied suggests that these results can be considered representative of TEMPOs reactivity toward all low-valent transition metal complexes.

Vibrational Cooling Dynamics of a [FeFe]-Hydrogenase Mimic Probed by Time-Resolved Infrared Spectroscopy

Picosecond time-resolved infrared spectroscopy (TRIR) was performed for the first time on a dithiolate bridged binuclear iron(I) hexacarbonyl complex ([Fe₂(μ-bdt)(CO)₆], bdt = benzene-1,2-dithiolate) which is a structural mimic of the active site of the [FeFe]-hydrogenase enzyme. As these model active sites are increasingly being studied for their potential in photocatalytic systems for hydrogen production, understanding their excited and ground state dynamics is critical. In n-heptane, absorption of 400 nm light causes carbonyl loss with low quantum yield (<10%), while the majority (ca. 90%) of the parent complex is regenerated with biexponential kinetics (τ₁ = 21 ps and τ₂ = 134 ps). In order to understand the mechanism of picosecond bleach recovery, a series of UV-pump TRIR experiments were performed in different solvents. The long time decay (τ₂) of the transient spectra is seen to change substantially as a function of solvent, from 95 ps in THF to 262 ps in CCl₄. Broadband IR-pump TRIR experiments were performed for comparison. The measured vibrational lifetimes (T₁(avg)) of the carbonyl stretches were found to be in excellent correspondence to the observed τ₂ decays in the UV-pump experiments, signifying that vibrationally excited carbonyl stretches are responsible for the observed longtime decays. The fast spectral evolution (τ₁) was determined to be due to vibrational cooling of low frequency modes anharmonically coupled to the carbonyl stretches that were excited after electronic internal conversion. The results show that cooling of both low and high frequency vibrational modes on the electronic ground state give rise to the observed picosecond TRIR transient spectra of this compound, without the need to invoke electronically excited states.

Insights into the photochemical disproportionation of transition metal dimers on the picosecond time scale.

The reactivity of five transition metal dimers toward photochemical, in-solvent-cage disproportionation has been investigated using picosecond time-resolved infrared spectroscopy. Previous ultrafast studies on [CpW(CO)3]2 established the role of an in-cage disproportionation mechanism involving electron transfer between 17- and 19-electron radicals prior to diffusion out of the solvent cage. New results from time-resolved infrared studies reveal that the identity of the transition metal complex dictates whether the in-cage disproportionation mechanism can take place, as well as the more fundamental issue of whether 19-electron intermediates are able to form on the picosecond time scale. Significantly, the in-cage disproportionation mechanism observed previously for the tungsten dimer does not characterize the reactivity of four out of the five transition metal dimers in this study. The differences in the ability to form 19-electron intermediates are interpreted either in terms of differences in the 17/19-electron equilibrium or of differences in an energetic barrier to associative coordination of a Lewis base, whereas the case for the in-cage vs diffusive disproportionation mechanisms depends on whether the 19-electron reducing agent is genuinely characterized by 19-electron configuration at the metal center or if it is better described as an 18 + δ complex. These results help to better understand the factors that dictate mechanisms of radical disproportionation and carry implications for radical chain mechanisms.

Direct observation of a bent carbonyl ligand in a 19-electron transition metal complex.

The photochemistry of [CpRu(CO)2]2 in P(OMe)3/CH2Cl2 solution has been studied using picosecond time-resolved infrared (TRIR) spectroscopy. Photolysis at 400 nm leads to the formation of 17-electron CpRu(CO)2(•) radicals, which react on the picosecond time scale to form 19-electron CpRu(CO)2P(OMe)3(•) adducts. The TRIR spectra of this adduct display an unusually low CO stretching frequency for the antisymmetric CO stretching mode, suggesting that one carbonyl ligand adopts a bent configuration to avoid a 19-electron count at the metal center. This spectral assignment is supported by analogous experiments on [CpFe(CO)2]2 in the same solvent, combined with DFT studies on the structures of the 19-electron adducts. The DFT results predict a bent CO ligand in CpRu(CO)2P(OMe)3(•), whereas approximately linear Fe-C-O bond angles are predicted for CpFe(CO)2P(OMe)3(•). The observation of a bent CO ligand in the 19-electron ruthenium adduct is a surprising result, and it provides new insight into the solution-phase behavior of 19-electron complexes. TRIR spectra were also collected for [CpRu(CO)2]2 in neat CH2Cl2, and it is interesting to note that no singly bridged [CpRu(CO)]2(μ-CO) photoproduct was observed to form following 400- or 267-nm excitation, despite previous observations of this species on longer time scales.

Studying the Dynamics of Photochemical Reactions via Ultrafast Time-Resolved Infrared Spectroscopy of the Local Solvent

Conventional ultrafast spectroscopic studies on the dynamics of chemical reactions in solution directly probe the solute undergoing the reaction. We provide an alternative method for probing reaction dynamics via monitoring of the surrounding solvent. When the reaction exchanges the energy (in form of heat) with the solvent, the absorption cross sections of the solvents infrared bands are sensitive to the heat transfer, allowing spectral tracking of the reaction dynamics. This spectroscopic technique was demonstrated to be able to distinguish the differing photoisomerization dynamics of the trans and cis isomers of stilbene in acetonitrile solution. We highlight the potential of this spectroscopic approach for studying the dynamics of chemical reactions or other heat transfer processes when probing the solvent is more experimentally feasible than probing the solute directly.

Spectroscopic Signature for Stable β-Amyloid Fibrils versus β-Sheet-Rich Oligomers

We use two-dimensional IR (2D IR) spectroscopy to explore fibril formation for the two predominant isoforms of the β-amyloid (Aβ1-40 and Aβ1-42) protein associated with Alzheimers disease. Two-dimensional IR spectra resolve a transition at 1610 cm-1 in Aβ fibrils that does not appear in other Aβ aggregates, even those with predominantly β-sheet-structure-like oligomers. This transition is not resolved in linear IR spectroscopy because it lies under the broad band centered at 1625 cm-1, which is the traditional infrared signature for amyloid fibrils. The feature is prominent in 2D IR spectra because 2D lineshapes are narrower and scale nonlinearly with transition dipole strengths. Transmission electron microscopy measurements demonstrate that the 1610 cm-1 band is a positive identification of amyloid fibrils. Sodium dodecyl sulfate micelles that solubilize and disaggregate preaggregated Aβ samples deplete the 1625 cm-1 band but do not affect the 1610 cm-1 band, demonstrating that the 1610 cm-1 band is due to very stable fibrils. We demonstrate that the 1610 cm-1 transition arises from amide I modes by mutating out the only side-chain residue that could give rise to this transition, and we explore the potential structural origins of the transition by simulating 2D IR spectra based on Aβ crystal structures. It was not previously possible to distinguish stable Aβ fibrils from the less stable β-sheet-rich oligomers with infrared light. This 2D IR signature will be useful for Alzheimers research on Aβ aggregation, fibril formation, and toxicity.