Reliable experimental method for determination of photoacidity revealed by quantum chemical calculations.

Photoacids are aromatic acids that exhibit significantly different acidities when they are electronically excited. Three experimental methods have been extensively used to determine the photoacidity, : fluorescence titration, the Förster cycle, and time-resolved experiments. However, the photoacidities determined by these experimental methods are not consistent. In this work, we used a theoretical method to evaluate the reliability of experimentally determined values. In particular, density functional theory (DFT) and time-dependent DFT calculations were used to obtain the changes in Gibbs free energy for acid dissociation reactions which are directly related to values. The Förster cycle, which is frequently used to experimentally determine the photoacidity due to its simplicity, yielded inconsistent results depending on how the transition energy was defined. We evaluated six empirical parameters extracted from the absorption and emission spectra of acidic and basic species of photoacids to adequately define the transition energy in the Förster cycle. And we found that the values obtained using the optical bandgap as the transition energy in the Förster cycle were in the best agreement with the results of quantum chemical calculations.

Beyond Woodward-Fieser Rules: Design Principles of Property-Oriented Chromophores Based on Explainable Deep Learning Optical Spectroscopy.

An adequate understanding of molecular structure-property relationships is important for developing new molecules with desired properties. Although deep learning optical spectroscopy (DLOS) has been successfully applied to predict the optical and photophysical properties of organic chromophores, how specific functional groups and solvents affect the optical properties is not clearly understood. Here, we employed an explainable DLOS method by applying the integrated gradients method to DLOS. The integrated gradients method allows us to obtain attributions, indicating how much the functional group contributes to the optical properties including the absorption wavelength and bandwidth, extinction coefficients, emission wavelength and bandwidth, photoluminescence quantum yield, and lifetime. The attributions of 54 functional groups and 9 solvent molecules to seven optical properties are quantified and can be used to estimate the optical properties of chromophores as in the Woodward-Fieser rule. Unlike the Woodward-Fieser rule for only the absorption wavelength, the attributions obtained in this work can be applied to estimate all seven optical properties, which makes a significant extension of the Woodward-Fieser rules. In addition, we demonstrated a strategy for utilizing the attributions in the design of molecules and in tuning the optical properties of the molecules. The design of molecular structures using attributions can revolutionize the development of optimal molecules.

Pyridine-NBD: A homocysteine-selective fluorescent probe for glioblastoma (GBM) diagnosis based on a blood test.

The precise in vitro diagnosis requires a high selectivity and sensitivity for a diagnostic agent. In this respect, fluorescent diagnostic probes have attracted attention in various clinical fields. Herein, we disclosed a tailor-made fluorescent homocysteine probe (NPO-Pyr) based on pyridine-thiol coordination and amine-addition. To date, Hcy has been recognized as an excellent biomarker for various diseases, but there still remain some limitations in detecting of Hcy due to its structural similarity to Cys. In this study, we developed a new fluorescent diagnostic probe for monitoring Hcy by incorporating 4-hydroxy-pyridine moiety into the skeleton of the NBD fluorophore. The incorporated pyridine moiety could coordinate with the thiol group at Hcy, followed by the amine-addition reaction (12 kJ/mol). Based on this rationale, NPO-Pyr responded to Hcy and exhibited turn-on properties with high selectivity and sensitivity (LOD: 0.084 ppm), and a fast-response time (<5 min). Furthermore, NPO-Pyr could predict the formation of glioblastoma (GBM) at an early stage through sensing Hcy in blood plasma (vs. healthy group, ∗∗∗∗P < 0.0001). Our findings have a significant importance across various fields from basic science to clinical translation, and we strongly believe that NPO-Pyr has the potential to fully replace the current complex GBM diagnostic process as a simpler in vitro agent.

Deep Learning Optical Spectroscopy Based on Experimental Database: Potential Applications to Molecular Design.

Accurate and reliable prediction of the optical and photophysical properties of organic compounds is important in various research fields. Here, we developed deep learning (DL) optical spectroscopy using a DL model and experimental database to predict seven optical and photophysical properties of organic compounds, namely, the absorption peak position and bandwidth, extinction coefficient, emission peak position and bandwidth, photoluminescence quantum yield (PLQY), and emission lifetime. Our DL model included the chromophore-solvent interaction to account for the effect of local environments on the optical and photophysical properties of organic compounds and was trained using an experimental database of 30 094 chromophore/solvent combinations. Our DL optical spectroscopy made it possible to reliably and quickly predict the aforementioned properties of organic compounds in solution, gas phase, film, and powder with the root mean squared errors of 26.6 and 28.0 nm for absorption and emission peak positions, 603 and 532 cm-1 for absorption and emission bandwidths, and 0.209, 0.371, and 0.262 for the logarithm of the extinction coefficient, PLQY, and emission lifetime, respectively. Finally, we demonstrated how a blue emitter with desired optical and photophysical properties could be efficiently virtually screened and developed by DL optical spectroscopy. DL optical spectroscopy can be efficiently used for developing chromophores and fluorophores in various research areas.

Ligand-Assisted Direct Photolithography of Perovskite Nanocrystals Encapsulated with Multifunctional Polymer Ligands for Stable, Full-Colored, High-Resolution Displays.

Micropatterns with a high stability, definition, and resolution are an absolute requirement in advanced display technology. Herein, patternable perovskite nanocrystals (PNCs) with excellent stability were prepared by exchanging pristine ligands with multifunctional polymer ligands, poly(2-cinnamoyloxyethyl methacrylate). The polymer backbone contains a cinnamoyl group that has been widely employed as a photo-cross-linker under 365 nm UV irradiation. Also, the terminal group is readily adjustable among NH3Cl, NH3Br, and NH3I, allowing us to obtain multicolored PNCs via instant anion exchange. Furthermore, the resulting ligand exchanged PNCs exhibited enhanced stability toward polar solvents without any undesirable influence on the structural or optical properties of the PNCs. Using anion exchanged PNCs, RGB microarrays with a subpixel size of 10 µm × 40 µm were successfully demonstrated. Our results highlight the versatility and feasibility of a simplified patterning strategy for nanomaterials, which can be generally applied in the fabrication of various optoelectronic devices.

Light-directed trapping of metastable intermediates in a self-assembly process.

Self-assembly is a dynamic process that often takes place through a stepwise pathway involving formation of kinetically favored metastable intermediates prior to generation of a thermodynamically preferred supramolecular framework. Although trapping intermediates in these pathways can provide significant information about both their nature and the overall self-assembly process, it is a challenging venture without altering temperature, concentrations, chemical compositions and morphologies. Herein, we report a highly efficient and potentially general method for "trapping" metastable intermediates in self-assembly processes that is based on a photopolymerization strategy. By employing a chiral perylene-diimide possessing a diacetylene containing an alkyl chain, we demonstrated that the metastable intermediates, including nanoribbons, nanocoils and nanohelices, can be effectively trapped by using UV promoted polymerization before they form thermodynamic tubular structures. The strategy developed in this study should be applicable to naturally and synthetically abundant alkyl chain containing self-assembling systems.

Experimental database of optical properties of organic compounds.

Experimental databases on the optical properties of organic chromophores are important for the implementation of data-driven chemistry using machine learning. Herein, we present a series of experimental data including various optical properties such as the first absorption and emission maximum wavelengths and their bandwidths (full width at half maximum), extinction coefficient, photoluminescence quantum yield, and fluorescence lifetime. A database of 20,236 data points was developed by collecting the optical properties of organic compounds already reported in the literature. A dataset of 7,016 unique organic chromophores in 365 solvents or in solid state is available in CSV format.

Penta-fluorophenol: a Smiles rearrangement-inspired cysteine-selective fluorescent probe for imaging of human glioblastoma.

Two of the most critical factors for the survival of glioblastoma (GBM) patients are precision diagnosis and the tracking of treatment progress. At the moment, various sophisticated and specific diagnostic procedures are being used, but there are relatively few simple diagnosis methods. This work introduces a sensing probe based on a turn-on type fluorescence response that can measure the cysteine (Cys) level, which is recognized as a new biomarker of GBM, in human-derived cells and within on-site human clinical biopsy samples. The Cys-initiated chemical reactions of the probe cause a significant fluorescence response with high selectivity, high sensitivity, a fast response time, and a two-photon excitable excitation pathway, which allows the imaging of GBM in both mouse models and human tissue samples. The probe can distinguish the GBM cells and disease sites in clinical samples from individual patients. Besides, the probe has no short or long-term toxicity and immune response. The present findings hold promise for application of the probe to a relatively simple and straightforward following of GBM at clinical sites.

Direct Photolithographic Patterning of Colloidal Quantum Dots Enabled by UV-Crosslinkable and Hole-Transporting Polymer Ligands.

Quantum dot (QD)-based displays call for nondestructive, high-throughput, and high-resolution patterning techniques with micrometer precision. In particular, self-emissive QD-based displays demand fine patterns of conductive QD films with uniform thickness at the nanometer scale. To meet these requirements, we functionalized QDs with photopatternable and semiconducting poly(vinyltriphenylamine-random-azidostyrene) (PTPA-N3-SH) ligands in which hole-transporting triphenylamine and UV-crosslinkable azide (-N3) groups are integrated. The hybridized QD films undergo chemical crosslinking upon UV irradiation without loss in the luminescence efficiency, enabling micrometer-scale QD patterns (pitch size down to ∼10 µm) via direct photolithography. In addition, the conjugated moieties in the ligands allow the crosslinked QD films to be used in electrically driven light-emitting diodes (LED). As the ultimate achievement, a patterned QD-LED was prepared with a maximum luminance of 11 720 cd m-2 and a maximum external quantum efficiency (EQE) of 6.25%. The present study offers a simple platform to fabricate conductive nanoparticle films with micrometer-scale patterns, and thus we anticipate that this system will expedite the realization of QD-based displays and will also be applicable to the manufacture of nanoparticles for other electronic devices.

Covalently Linked Perylene Diimide-Polydiacetylene Nanofibers Display Enhanced Stability and Photocurrent with Reversible FRET Phenomenon.

Because of their unique structural and optical properties, 1D perylene diimide (PDI) derivatives have gained attention for use in optoelectronic devices. However, PDI-containing self-assembled supramolecular systems often are of limited use because they have supramolecular architectures that are held together by weak noncovalent π-π stacking, hydrogen bonding, and hydrophobic interactions. As a result, they are intrinsically unstable under solution-processing conditions. To overcome this limitation, a polydiacetylene (PDA)-based strategy is developed to construct a solvent-resistant and stable PDI assembly. For this purpose, first the monomer PDI-BisDA is generated, in which two polymerizable diacetylene (DA) units are covalently linked to a PDI core. Importantly, 254 nm UV irradiation of self-assembled PDI-BisDA nanofibers forms solvent-resistant and stable PDI-PDA fibers. Owing to the presence of PDA, the generated polymer fibers display an increased photocurrent. In addition, the existence of PDA and PDI moieties in the fiber leads to the occurrence of switchable on-off fluorescence resonance energy transfer (FRET) between the PDI and reversibly thermochromic PDA chromophores.

A naphthoimidazolium-cholesterol derivative as a ratiometric fluorescence based chemosensor for the chiral recognition of carboxylates.

Fluorescent chemosensors for sensing chiral molecules have been actively studied in recent years. In the current study, we report a naphthoimidazolium-cholesterol derivative (NI-chol 1) as a fluorescence based chemosensor for chiral recognition, in which the naphthoimidazolium serves not only as a fluorophore but also as a recognition moiety for anions via imidazolium (C-H)+-anion binding and the cholesterol unit acts as a chiral barrier. In particular, NI-chol 1 displayed unique and distinct ratiometric changes with Boc-d-Phe, on the other hand, Boc-l-Phe induced a negligible change. Furthermore, a distinct downfield shift (from 9.64 ppm to 9.96 ppm) of the imidazolium C-H peak was observed for Boc-d-Phe (5 eq.) with severe broadening, which indicates strong ionic hydrogen bonding between the C-H proton and the carboxylate.

Elucidating the Role of Molecule-Electrode Interfacial Defects in Charge Tunneling Characteristics of Large-Area Junctions.

Interfacial chemistry at organic-inorganic contact critically determines the function of a wide range of molecular and organic electronic devices and other systems. The chemistry is, however, difficult to understand due to the lack of easily accessible in-operando spectroscopic techniques that permit access to interfacial structure on a molecular scale. Herein, we compare two analogous junctions formed with identical organic thin film and different liquid top-contacts (water droplet vs eutectic gallium indium alloy) and elucidate the puzzling interfacial characteristics. Specifically, we fine-tune the surface topography of the organic surface using mixed self-assembled monolayers (SAMs): single component SAM composed of rectifier (2,2'-bipyridyl-terminated n-undecanethiolate; denoted as SC11BIPY) is systematically diluted with nonrectifying n-alkanethiolates of different lengths (denoted as SC n where n = 8, 10, 12, 14, 16, 18). Characterization of the resulting mixed SAMs in wettability and tunneling currents with the two separate liquid top-contacts allows us to investigate the role of phase segregation and gauche defect in the SAM//liquid interfaces. The results reported here show the difference in length between SC11BIPY and SC n is translated into nanoscopic pits and gauche-conformer defects on the surface, and the difference in contact force-hydrostatic vs user pressures-and hence conformity of contact account for the difference in wettability and rectification behaviors. Our work provides an insight into the role of molecule-electrode interfacial defects in performance of molecular-scale electronic devices.

Cationic Effect on the Equilibria and Kinetics of the Excited-State Proton Transfer Reaction of a Photoacid in Aqueous Solutions.

Dissolved ions have a significant effect on the chemical equilibria and kinetics in aqueous solutions by changing the physical properties and hydrogen bond network of water. In this work, the ionic effects on the excited-state proton transfer (ESPT) reactions of Coumarin 183 (C183) in aqueous ionic solutions are comprehensively studied in terms of p Ka, p Ka*, activation energies, and kinetic isotope effect (KIE). The acid dissociation constants (p Ka and p Ka*) of C183 on the ground and excited states are determined by UV-visible absorption and steady-state fluorescence spectroscopy. The activation energies ( Ea) and KIE for the ESPT reaction of C183 are directly obtained by time-resolved fluorescence spectroscopy. The changes in p Ka, p Ka*, Ea, and KIE values of C183 are found to be dependent on the charge density of cations. The secondary KIE is more substantially influenced by the dissolved ions than the primary KIE. Furthermore, the ionic effects on the equilibrium (p Ka and p Ka*) and kinetic ( Ea and KIE) parameters of C183 are found to be well-explained by the free-energy reactivity relation. Our current results are very important in understanding the ionic effects on the equilibria and ESPT kinetics of photoacids in aqueous ionic solutions.

Ionic effects on the proton transfer mechanism in aqueous solutions.

Proton dissociation (PD) reactions of weak acids and proton transfer (PT) processes in aqueous solutions are strongly influenced by ions. However, a detailed molecular picture that describes how ions affect the rates of PD and PT processes is still missing. Here, we utilize time-resolved fluorescence spectroscopy combined with quantum chemical calculations to investigate the excited-state proton transfer (ESPT) reaction of a photoacid in aqueous metal chloride solutions. The activation energy (Ea) for the ESPT of the photoacid increases with increasing charge density of cations (ρcat). The local hydrogen bond (H-bond) structure of the photoacid in the ionic hydration shell is strongly related to both the Ea and the ρcat. Most importantly, the proton's positive charge in the transition state, which is delocalized through the H-bonded water channel, is more destabilized with an increase in the ρcat, leading to a higher Ea. Our experimental and computational results allow us to elucidate the underlying mechanism for the ionic effect on PD and the subsequent PT process at the molecular level.

Photoinduced reversible phase transition of azobenzene-containing polydiacetylene crystals.

An azobenzene-containing supramolecular polydiacetylene (PDA) crystal undergoes a photoinduced reversible blue-to-red phase transition accompanied by crystal tearing.

Electronic relaxation dynamics of PCDA-PDA studied by transient absorption spectroscopy.

Photo-curable polymers originating from 10,12-pentacosadiynoic acid (PCDA-PDA) are commonly used polydiacetylenes (PDAs). PCDA-PDA exhibits thermochromic properties undergoing a unique colorimetric transition from blue to red as the temperature is increased from low to high. In this work, we have carefully studied the temperature-dependent optical properties of PCDA-PDA by using UV-visible absorption, FTIR, Raman, and transient absorption (TA) spectroscopy in combination with quantum chemical calculations. Temperature-dependent UV-visible absorption spectra indicate that PCDA-PDA exhibits reversible thermochromic properties up to 60 °C and its thermochromic properties become irreversible above 60 °C. Such distinct thermochromic properties are also manifested in TA signals so that the electronically excited PCDA-PDA relaxes to the ground state via an intermediate state at 20 °C (blue form) but it relaxes directly back to the ground state at 80 °C (red form). The electronic relaxation dynamics of PCDA-PDA are comprehensively analyzed based on different kinetic models by using the global fitting analysis method. The intermediate state in the blue form of PCDA-PDA is clearly found to be responsible for fluorescence quenching. FTIR and Raman spectroscopy and quantum chemical calculations confirm that the H-bonds between the carboxylic acid groups in PCDA-PDA are broken at high temperatures leading to an irreversible structural change of PCDA-PDA.

Origin of the Reversible Thermochromic Properties of Polydiacetylenes Revealed by Ultrafast Spectroscopy.

Polydiacetylenes (PDAs) with thermochromic properties undergo colorimetric transitions when the external temperature is varied. This capability has the potential to enable these materials to be used as temperature sensors. These thermochromic properties of PDAs stem from their temperature-dependent optical properties. In this work, we studied the temperature-dependent optical properties of Bis-PDA-Ph, which exhibits reversible thermochromic properties, and PCDA-PDA, which exhibits irreversible thermochromic properties, by UV-visible absorption and femtosecond transient absorption spectroscopy. Our results indicate that the electronic relaxation of PDAs occurs via an intermediate state in cases where the material exhibits reversible thermochromic properties, whereas the excited PDAs relax directly back to the ground state when irreversible thermochromic properties are observed. The existence of this intermediate state in the electronic relaxation of PDAs thus plays an important role in determining their thermochromic properties. These results are very important for both understanding and strategically modulating the thermochromic properties of PDAs.

Effect of NaCl Salts on the Activation Energy of Excited-State Proton Transfer Reaction of Coumarin 183.

Coumarin 183 (C183) was used as a photoacid to study excited-state proton transfer (ESPT) reactions. Here, we studied the effect of ions on the ESPT of C183 in aqueous NaCl solutions using a steady-state fluorescence spectroscopy and time-correlated single photon counting (TCSPC) method. The acid dissociation equilibrium of excited-state C183 and the activation energy for the ESPT of C183 were determined as a function of NaCl concentration. The change in the equilibrium constant was found to be correlated with the solvation energy of deprotonated C183. Frequency-resolved TCSPC signals measured at several temperatures were analyzed by using a global fitting analysis method which enabled us to extract all the rate constants involving the ESPT reaction and the spectra of individual species. The activation energy for the ESPT reaction of C183 was highly dependent on NaCl concentration. Quantum chemical calculations were used to calculate the local hydrogen-bond (H-bond) configurations around C183 in aqueous NaCl solutions. It was found that the activation energy for the ESPT was determined by the local H-bond configurations around C183 which were significantly influenced by the dissolved ions.