Steady-state Absorption Research Articles

Symmetric dicyanobenzothiadiazole (DCBT) dyes with a 1.5 eV excited state reduction potential range.

Strong molecular photooxidants are important in many disciplines including organic synthesis and renewable energy. In these fields, strongly oxidizing chromophores are employed to drive various transformations from challenging bond formations to energy storage systems. A range of photooxidant strengths are needed to drive these processes. A series of 8 symmetrically bisarylated 5,6-dicyano[2,1,3]benzothiadiazole (DCBT) dyes were studied for their tunability toward breadth of light absorption and photooxidant strength. The dye oxidation strength and light absorption tunability is the result of appending various aryl substituents on the periphery of the DCBT core which shows remarkable tunability of the final chromophore. The dyes are studied via steady-state absorption and emission, time-correlated single photon counting, computational analysis, and cyclic voltammetry. In changing the peripheral aryl substituents via electronics, sterics, and π-conjugation length, a series of dyes are arrived at with a dramatic 1.5 eV range in oxidizing strength and >200 nm (0.95 eV) absorption maxima tunability. Furthermore, two dyes in the series exhibit strong oxidizing strength while still approaching red light absorbance (>650 nm onset) which provides unique opportunities for the use of lower energy light to affect chemical transformations. Ultimately, this series provides options for photooxidations that allow for energetic tuning and selectivity for a given chemical transformation.

Origin of the low-energy tail in the photoluminescence spectrum of CsPbBr3 nanoplatelets: a femtosecond transient absorption spectroscopic study.

CsPbBr3 nanoplatelets (NPLs), as some of the two-dimensional lead halide perovskites, have been intensively investigated due to their outstanding photophysical and photoelectric properties. However, there remain unclear fundamental issues on their carrier kinetics and the low-energy tail in their photoluminescence (PL) spectrum. In this paper, we synthesized CsPbBr3 NPLs with five [PbBr6]4- monolayers and performed comprehensive studies by using steady-state absorption, PL, and femtosecond transient absorption (fs-TA) spectroscopic measurements. We determined both the biexciton Auger recombination time (7 ± 2 ps) and trapped exciton lifetime (110 ± 15 ps) of the five monolayer CsPbBr3 NPLs. We also investigated the origin of the low-energy tail emission in their PL spectrum. More importantly, we found that a negative ΔA feature in the energy range of 2.45-2.55 eV appears in their fs-TA spectrum at 2, 4 and 10 ps delay times, which could help them act as a laser gain medium. The low-energy tail emission in their PL spectrum overlaps well with the negative ΔA feature in the energy range of 2.45-2.55 eV in their fs-TA spectrum at 2, 4 and 10 ps delay times.

NIR light-triggered photodynamic antibacterial nanofiber membrane based on polycaprolactone and phthalocyanine derivative for biomedical applications.

Photodynamic therapy (PDT) is gaining recognition as a promising alternative method for the treatment of diverse biomedical applications. Toward this goal, we report herein the fabrication of an electrospun membrane utilizing polycaprolactone (PCL), and a phthalocyanine derivative, namely 1,4,8,11,15,22,25-octabutyloxy-29H,31-phthalocyanine (OBuPc). The designed OBuPc-PCL membrane aims to function as a dressing with the potential to facilitate the management of wound healing. The absorption and fluorescence studies of OBuPc have been examined by the steady-state and time-resolved absorption and fluorescence techniques. From direct detection of the weak emission of the singlet oxygen in the NIR region (at 1270 nm), the quantum yield of singlet oxygen was determined to be 0.05. The physiochemical properties of the nanofibers and membranes that were prepared were determined. The photo-activity of all the modified PCL nanofibers against Gram-positive S. aureus and Gram-negative E. coli was observed. The PCL/4.8 OBuPc nanofiber exhibited the highest effectiveness, primarily attributed to the enhanced effect of photosensitizer OBuPc as its concentration increased within the fibre. This resulted in S. aureus bacterial inhibition% of 62.5% ± 0.38 and 78.5% ± 0.49 after exposure to near infrared emission NIR at 630 nm for 15 minutes and 30 minutes, respectively. The inhibition of E. coli bacteria was observed to be 51.51% ± 0.49 and 62.44% ± 0.12% after exposure to near infrared (NIR) emission at a wavelength of 630 nm for durations of 15 minutes and 30 minutes, respectively. Additionally, it was observed that the membranes displayed dark bacterial inhibition. These unique features of the examined nanofibers render them a potential photodynamic antibacterial nanofiber membrane for efficient wound healing treatment and practical antibacterial uses.

Porphyrins on acid: kinetics of the photoinduced-protonation of tetrakis(4-carboxyphenyl)-porphyrin.

Free-base porphyrins can be protonated, which significantly impacts their electronic and excited state properties. While excited state dynamics are well explored for either neutral or fully protonated porphyrins, the intermediate region has not yet been explored, although their potential implications for photocatalytic reactions are evident. This study explores how partial protonation affects the nature and properties of photoexcited states of tetrakis(4-carboxyphenyl)porphyrin (TCPP) using steady-state and nanosecond transient absorption spectroscopy. Global-fit analysis of the decay curves revealed the formation of a protonated excited triplet state from the neutral triplet state, as well as the long lifetimes of these species of up to 120 μs. The photoexcited triplet state of TCPP functions as a photobase, which was confirmed by computational analysis of the electron density of the exited states showing increased nucleophilicity at the unprotonated nitrogen atoms of the porphyrin core. These findings indicate that photoinduced protonated excited triplet states can function as electron acceptors with anodically shifted redox potentials, opening new pathways for porphyrin-based photoreactions.

Solvent effects on the intramolecular charge transfer excited state of 3CzClIPN: a broadband transient absorption study.

The prediction of solvent properties using molecular probes often relies on correlating steady-state absorption and fluorescence measurements, as well as determining absorption maxima and/or Stokes shifts. In this study, we employ femtosecond broadband transient absorption (fs-bb-TA) spectroscopy to investigate the spectroscopic behaviour of the intramolecular charge transfer (ICT) excited state of 3CzClIPN (2,4,6-tri(9H-carbazol-9-yl)-5-chloroisophthalonitrile), a representative ICT organic molecule, in both aromatic and non-aromatic solvents. Unlike observations in non-aromatic media, fs-bb-TA spectra of 3CzClIPN in aromatic solvents exhibit enhanced spectral broadening that strongly correlates with the solvent's polarity. We hypothesise that this spectral broadening originates from a wider configurational energy landscape experienced by the positively charged carbazole Cz+ group, owing to the larger size and, consequently, reduced solvation effectiveness of aromatic solvent molecules.

Visible-Light-Activated Carbon Monoxide Release from Porphyrin-Flavonol Hybrids.

We report on porphyrin-flavonol hybrids consisting of a porphyrin antenna and four covalently bound 3-hydroxyflavone (flavonol) groups, which act as highly efficient photoactivatable carbon monoxide (CO)-releasing molecules (photoCORMs). These bichromophoric systems enable activation of the UV-absorbing flavonol chromophore by visible light up to 650 nm and offer precise spatial and temporal control of CO administration. The physicochemical properties of the porphyrin antenna system can also be tuned by inserting a metal cation. Our computational study revealed that the process occurs via endergonic triplet-triplet energy transfer from porphyrin to flavonol and may become feasible thanks to flavonol energy stabilization upon intramolecular proton transfer. This mechanism was also indirectly supported by steady-state and transient absorption spectroscopy techniques. Additionally, the porphyrin-flavonol hybrids were found to be biologically benign. With four flavonol CO donors attached to a single porphyrin chromophore, high CO release yields, excellent uncaging cross sections, low toxicity, and CO therapeutic properties, these photoCORMs offer exceptional potential for their further development and future biological and medical applications.

Solution-based Supramolecular Hierarchical Assembly of Frenkel Excitonic Nanotubes Driven by Gold Nanoparticle Formation and Temperature.

Translating nature's successful design principle of solution-based supramolecular self-assembling to broad applications─ranging from renewable energy and information technology to nanomedicine─requires a fundamental understanding of supramolecular hierarchical assembly. Though the forces behind self-assembly (e.g., hydrophobicity) are known, the specific mechanism by which monomers form the hierarchical assembly still remains an open question. A crucial step toward formulating a complete mechanism is understanding not only how the monomer's specific molecular structure but also how manifold environmental conditions impact the self-assembling process. Here, we elucidate the complex correlation between the environmental self-assembling conditions and the resulting structural properties by utilizing a well-characterized model system: well-defined supramolecular Frenkel excitonic nanotubes (NTs), self-assembled from cyanine dye molecules in aqueous solution, which further self-assemble into bundled nanotubes (b-NTs). The NTs and b-NTs inhabit distinct spectroscopic signatures, which allows the use of steady-state absorption spectroscopy to monitor the transition from NTs to b-NTs directly. Specifically, we investigate the impact of temperature (ranging from 23 °C, 55 °C, 70 °C, 85 °C, up to 100 °C) during in situ formation of gold nanoparticles to determine their role in the formation of b-NTs. The considered time regime for the self-assembling process ranges from 1 min to 8 days. With our work, we contribute to a basic understanding of how environmental conditions impact solution-based hierarchical supramolecular self-assembly in both the thermodynamic and the kinetic regime.

N-Type Fullerene-Carbon Dots: Synthesis and Electrochemical and Photophysical Properties.

The covalent incorporation of C60 and C70 derivatives of the well-known n-type organic semiconductor PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) onto carbon dots (CD) is described. Morphological and structural characterization reveal combined features of both pristine starting materials (CD and PCBM). Electrochemical investigations evidenced the existence of additional reduction processes to that of CD or PCBM precursors, showing rich electron-acceptor capabilities, with multistep processes in an affordable and narrow electrochemical window (ca. 1.5 V). Electronic communication in the obtained nanoconjugated species were derived from steady-state absorption and emission spectroscopies, which showed bathochromically shifted absorptions and emissions well entering the red region. Finally, the lower fluorescence quantum yield of CD-PCBM nanoconjugates, compared with CD, and the fast decay of the observed emission of CD, support the existence of an electronic communication between both CD and PCBM units in the excited state.

Spectral characteristics of the flavones and anthocyanins present in passionflower (Passiflora incarnata).

Rich in antioxidants with a variety of flavones and anthocyanins, passionflower/fruit has been extensively used in food, beverage, medicinal, and natural dyes industries. The individual components present in passionflower are identified by extracting them in methanol, partitioning them between ethyl acetate and aqueous layers, and recording their ESI mass spectrometric data. The steady-state absorption and fluorescence spectra of the extract in methanol and dimethyl sulfoxide are recorded and the lifetime of the fluorescing species is reported. The pH dependence of the absorption spectrum confirms the presence of the anthocyanins.

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides.

2,2'-Bis(4-dimethylaminophenyl)- and 2,2'-dicyclohexyl-1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d]imidazole ((N-DMBI)2 and (Cyc-DMBI)2) are quite strong reductants with effective potentials of ca. -2 V vs ferrocenium/ferrocene, yet are relatively stable to air due to the coupling of redox and bond-breaking processes. Here, we examine their use in accomplishing electron transfer-induced bond-cleavage reactions, specifically dehalogenations. The dimers reduce halides that have reduction potentials less cathodic than ca. -2 V vs ferrocenium/ferrocene, especially under UV photoexcitation (using a 365 nm LED). In the case of benzyl halides, the products are bibenzyl derivatives, whereas aryl halides are reduced to the corresponding arenes. The potentials of the halides that can be reduced in this way, quantum-chemical calculations, and steady-state and transient absorption spectroscopy suggest that UV irradiation accelerates the reactions via cleavage of the dimers to the corresponding radical monomers.

New Twist on the Light-Switch Effect: Controlling the Fate of Excited States with pH in a 4-Hydroxy-thiazol-extended Ruthenium(II) Dppz Complex.

We present a pH-dependent study of the excited state dynamics of a novel Ru complex bearing a 4-hydroxy thiazol-substituted dppz (dipyridophenazine) ligand (RuTzOH) and its deprotonated form (RuTzO-). We combine steady-state and time-resolved absorption and emission spectroscopy with electrochemical investigations to characterize the excited state relaxation, which upon photoexcitation at 400 nm is determined by a multitude of initially populated MLCT states for both complexes. Subsequently, for RuTzOH, two long-lived excited states are populated, leading to dual emission from the complexes, a feature that vanishes upon deprotonation. Upon deprotonation, the electron density on the dppz moiety increases significantly, leading to rapid energy populating ligand-centered states and thus deactivating the initially excited MLCT states.

Photochemical Stability of 5-Methylcytidine Relative to Cytidine: Photophysical Insight for mRNA Therapeutic Applications.

5-Methylcytidine (5mCyd) has recently been investigated with renewed interest in its utilization in mRNA therapeutics. However, its photostability following exposure to electromagnetic radiation has been overlooked. This Letter compares the photostability and excited-state dynamics of 5mCyd with those of the canonical RNA nucleoside, cytidine (Cyd), using steady-state and femtosecond transient absorption spectroscopy under physiologic conditions. 5mCyd is shown to have a 5-fold higher fluorescence yield and a 5-fold longer 1ππ* excited-state decay lifetime. Importantly, however, the excited-state population in 5mCyd decays primarily by internal conversion, with a photodegradation rate 3 times smaller than that in Cyd. In Cyd, the population of a 1nπ* state with a lifetime of ca. 45 ps is implicated in the formation 6-hydroxycytidine and other photoproducts.

MCNOX: A code for computing and interpreting ultrafast nonlinear X-ray spectra of molecules at the multiconfigurational level

This work describes a program for computing and analyzing the ultrafast (attosecond and femtosecond) nonlinear X-ray spectra of molecules at the multiconfigurational quantum chemistry level, called MCNOX. It is aimed at cutting-edge current and future photochemistry/photophysics applications enabled by X-ray free-electron lasers and high harmonic generation light sources. It can compute steady-state X-ray absorption spectroscopy (XAS) and three types of ultrafast nonlinear X-ray spectra: transient XAS, all-X-ray four-wave mixing, and stimulated Raman spectra. It is especially capable of picking out major electronic transitions, and further computing the natural transition orbitals for these transitions, which help finally yield the physical and chemical insights from complex signals. Following a research paradigm of “electronic structure→molecular dynamics→signal”, in this paper, methods for the former two steps are reviewed, and then the theory, implementations, and technical details for signal simulations are presented along illustrative examples on uracil.

Time-resolved spectroscopic and computational study of the initial events in doxazosin photochemistry

Doxazosin is a quinazoline derivative widely used in medicine as a drug. In this study, a combined experimental and computational approach based on the time-dependent density functional theory was used to elucidate the primary events following the photoexcitation of DOX upon interaction with light. The photophysical properties and photochemical reactivity of DOX were investigated by steady-state and time-resolved absorption and fluorescence spectroscopy. DOX in H2O in S0 is present in two prototropic forms, with the protonated form dominating (∼91 %, pKa = 6.75). The computations indicated that the most basic quinazoline nitrogen is at the position 1. Upon excitation, DOX deprotonates in the singlet excited state (pKa* = 1.31), and the decay times from the singlet excited state of 5 ns and 13 ns are attributed to the non-protonated and protonated forms of DOX, respectively. The quantum yield of fluorescence in H2O is 0.51 and 0.64 in basic media. The quantum yield of intersystem crossing along with triplet–triplet molar absorption coefficient at 520 nm and the lifetime of the triplet excited state were obtained by LFP, ΦISC = 0.17, ε520 = 11600 ± 100 M−1 cm−1 and τ = 11 μs, respectively. Furthermore, LFP enabled detection of DOX radical formed by the photoinduced intramolecular electron transfer from the benzodioxane-carbamoyl to the protonated aminoquinazoline. Computations were used to back up the assignments of the detected transients and to construct an energy diagram with all plausible photophysical and photochemical pathways. These results elucidated the mechanisms of DOX photochemistry leading to DOX photodegradation which is relevant to environmental studies. They also provided insights into the potential use of such a quinazoline derivative in other applications such as push–pull chromophores or fluorescent probes.

Catalyzing Singlet Fission by Transition Metals: Second versus Third Row Effects.

The synthesis and characterization of platinum(II) and palladium(II) complexes bearing two (dimers Pt(Lpc)2Cl2 and Pd(Lpc)2Cl2), one (monomers Pt(Lpc)(Lref)Cl2 and Pd(Lpc)(Lref)Cl2), or no (reference compounds Pt(Lref)2Cl2 and Pd(Lref)2Cl2) pentacene-based pyridyl ligands are presented. Photophysical properties of the dimers are probed by means of steady-state and time-resolved transient absorption measurements in comparison to the monomer and model compounds. Our results document that despite enhanced spin-orbit coupling from the presence of heavy atoms, intramolecular singlet fission (iSF) is not challenged by intersystem crossing. iSF thus yields correlated triplet pairs and even uncorrelated triplet excited states upon decoherence. Importantly, significant separation of the two pentacenyl groups facilitates decoupling of the two chromophores. Furthermore, the mechanism of iSF is altered depending on the respective metal center, that is, Pt(II) versus Pd(II). The dimer based on Pt(II), Pt(Lpc)2Cl2, exhibits a direct pathway for the iSF and forms a correlated triplet pair with singlet-quintet spin-mixing within 10 ns in variable solvents. On the other hand, the dimer based on Pd(II), Pd(Lpc)2Cl2, leads to charge transfer mixing during the population of the correlated triplet pair that is dependent on solvent polarity. Moreover, Pd(Lpc)2Cl2 gives rise to a stable equilibrium between singlet and quintet correlated triplet pairs with lifetimes of up to 170 ns. Inherent differences in the size and polarizability, when contrasting platinum(II) with palladium(II), are the most likely rationale for the underlying trends.

Time-Resolved Spectroelectrochemical Dynamics of Carotenoid 8'-apo-β-Carotenal.

This work examines the influence of applied external voltage in bulk electrolysis on the excited-state properties of 8'-apo-β-carotenal in acetonitrile by steady-state and ultrafast time-resolved absorption spectroscopy. The data collected under bulk electrolysis were compared with those taken without applied voltage. The steady-state measurements showed that although intensity of the S0 -S2 absorption band varies with the applied voltage, the spectral position remain nearly constant. Comparison of transient absorption spectra shows that the magnitude of the ICT-like band decreases during the experiment under applied voltage condition, and is associated with a prolongation of the S1 /ICT-like lifetime from 8 ps to 13 ps. Furthermore, switching off the applied voltage resulted in returning to no-voltage data within about 30 min. Our results show that the amplitude of the signal associated with the ICT state can be tuned by applying an external voltage.

Energy transfer dynamics between carbon quantum dots and molybdenum disulfide revealed by transient absorption spectroscopy

Zero-dimensional environmentally friendly carbon quantum dots (CQDs) combined with two-dimensional materials have a wide range of applications in optoelectronic devices. We combined steady-state and transient absorption spectroscopies to study the energy transfer dynamics between CQDs and molybdenum disulfide (MoS2). Transient absorption plots showed photoinduced absorption and stimulated emission features, which involved the intrinsic and defect states of CQDs. Adding MoS2 to CQDs solution, the lowest unoccupied molecular orbital of CQDs transferred energy to MoS2, which quenched the intrinsic emission at 390 nm. With addition of MoS2, CQD-MoS2 composites quenched defect emission at 490 nm and upward absorption, which originated from another energy transfer from the defect state. Two energy transfer paths between CQDs and MoS2 were efficiently manipulated by changing the concentration of MoS2, which laid a foundation for improving device performance.

Elucidating the Excited State Behavior of Pyridyl Pyridinium Systems via Computational and Transient Absorption Studies of Tetrahedral Multichromophoric Arrays and their Model Compounds.

The tetrahedral shape-persistent molecule 14+ , containing four identical pyridyl pyridinium units connected via a sp3 hybridized carbon atom, has been investigated in detail by means of steady-state and time resolved spectroscopy. Remarkable photophysical properties are observed, particularly in comparison with protonated and methylated analogues (1H4 8+ , 1Me4 8+ ), which exhibit substantially shorter excited state lifetimes and lower emission quantum yields. Theoretical studies have rationalized the behavior of the tetrameric molecules relative to the monomers, with DFT and TD-DFT calculations corroborating steady-state (absorption and emission) and transient absorption spectra. The behavior of the monomeric compounds (each consisting in one of the four identical subunits of the tetramers, i. e., 2+ , 2H2+ and 2Me2+ ) considerably differs from that of the tetramers, indicating a strong electronic interaction between the subunits in the tetrameric species, likely promoted by the homoconjugation through the connecting sp3 C atom. 2+ is characterized by a peculiar S1 -S2 excited state inversion, whereas the short-lived emitting S1 state of 2H2+ and 2Me2+ exhibits a partial charge-transfer character, as substantiated by spectro-electrochemical studies. Among the six investigated systems, only 14+ is a sizeable luminophore (Φem =0.15), which is related to the peculiar features of its singlet state.

How good can a simple artificial neural network predict the medium reorganization energy and the free energy gap from a steady-state fluorescence spectrum?

Medium reorganization energy, Erm, and free energy gap, ΔG, are key characteristics in determining the photoinduced charge transfer rate. They are strongly related to the width and position of the steady-state fluorescence and absorption spectra of organic dyes in solvents. Steady-state spectroscopy is one of the most standard techniques for studying organic dyes. Here, we present a simple machine learning model for cost-effective prediction the medium reorganization energy and the free energy gap from the steady-state fluorescence spectra. Fluorescence spectra with corresponding reference values of physical quantities are calculated using an explicit mathematical expression that addresses electronic-vibrational transitions, intramolecular and solvent reorganizations. An approach to the separate formation of data sets for training and validation is proposed. Gaussian noise is used in training to improve predictions. This study shows that Erm and ΔG can be predicted with the mean absolute error ∼0.024 eV and ∼0.009 eV, respectively. Robustness testing is performed on the experimental spectra of coumarin-153, coumarin-307, and coumarin-522B in a series of solvents.

Trap or Triplet? Excited-State Interactions in 2D Perovskite Colloids with Chromophoric Cations.

Movement of energy within light-harvesting assemblies is typically carried out with separately synthesized donor and acceptor species, which are then brought together to induce an interaction. Recently, two-dimensional (2D) lead halide perovskites have gained interest for their ability to accommodate and assemble chromophoric molecules within their lattice, creating hybrid organic-inorganic compositions. Using a combination of steady-state and time-resolved absorption and emission spectroscopy, we have now succeeded in establishing the competition between energy transfer and charge trapping in 2D halide perovskite colloids containing naphthalene-derived cations (i.e., NEA2PbX4, where NEA = naphthylethylamine). The presence of room-temperature triplet emission from the naphthalene moiety depends on the ratio of bromide to iodide in the lead halide sublattice (i.e., x in NEA2Pb(Br1-xIx)4), with only bromide-rich compositions showing sensitized emission. Photoluminescence lifetime measurements of the sensitized naphthalene reveal the formation of the naphthalene triplet excimer at room temperature. From transient absorption measurements, we find the rate constant of triplet energy transfer (kEnT) to be on the order of ∼109 s-1. At low temperatures (77 K) a new broad emission feature arising from trap states is observed in all samples ranging from pure bromide to pure iodide composition. These results reveal the interplay between sensitized triplet energy transfer and charge trapping in 2D lead halide perovskites, highlighting the need to carefully parse contributions from competing de-excitation pathways for optoelectronic applications.