Dual Enhancement of Phosphorescence and Circularly Polarized Luminescence through Entropically Driven Self-Assembly of a Platinum(II) Complex.

Addressing the dual enhancement of circular polarization (glum) and luminescence quantum yield (QY) in circularly polarized luminescence (CPL) systems poses a significant challenge. In this study, we present an innovative strategy utilizing the entropically driven self-assembly of amphiphilic phosphorescent platinum(II) complexes (L-Pt) with tetraethylene glycol chains, resulting in unique temperature dependencies. The entropically driven self-assembly of L-Pt leads to a synergistic improvement in phosphorescence emission efficiency (QY was amplified from 15 % at 25 °C to 53 % at 60 °C) and chirality, both in the ground state and the excited state (glum value has been magnified from 0.04×10-2 to 0.06) with increasing temperature. Notably, we observed reversible modulation of phosphorescence and chirality observed over at least 10 cycles through successive heating and cooling, highlighting the intelligent control of luminescence and chiroptical properties by regulating intermolecular interactions among neighboring L-Pt molecules. Importantly, the QY and glum of the L-Pt assembly in solid state were measured as 69 % and 0.16 respectively, representing relatively high values compared to most self-assembled CPL systems. This study marks the pioneering demonstration of dual thermo-enhancement of phosphorescence and CPL and provides valuable insights into the thermal effects on high-temperature and switchable CPL materials.

Introducing Water-Network-Assisted Proton Transfer for Boosted Electrocatalytic Hydrogen Evolution with Cobalt Corrole.

Proton transfer is vital for many biological and chemical reactions. Hydrogen-bonded water-containing networks are often found in enzymes to assist proton transfer, but similar strategy has been rarely presented by synthetic catalysts. We herein report the Co corrole 1 with an appended crown ether unit and its boosted activity for the hydrogen evolution reaction (HER). Crystallographic and 1 H NMR studies proved that the crown ether of 1 can grab water via hydrogen bonds. By using protic acids as proton sources, the HER activity of 1 was largely boosted with added water, while the activity of crown-ether-free analogues showed very small enhancement. Inhibition studies by adding 1) external 18-crown-6-ether to extract water molecules and 2) potassium ion or N-benzyl-n-butylamine to block the crown ether of 1 further confirmed its critical role in assisting proton transfer via grabbed water molecules. This work presents a synthetic example to boost HER through water-containing networks.

Specific counter-cation effect on the molecular orientation of thiocyanate anions at the aqueous solution interface.

Understanding the interfacial structure of aqueous electrolyte solutions is important and relevant to a wide range of systems, ranging from atmospheric aerosols to electrochemistry, and biological environments. Though significant efforts have been made to unravel the interfacial structure of water molecules, the structure and dynamics of ions at the interface have not yet been fully elucidated. Here, the interfacial structure of the aqueous solution was investigated directly by monitoring the thiocyanate (SCN-) anions using surface-specific sum frequency generation (SFG) vibrational spectroscopy. The molecular orientation of the SCN- anions and their adsorption behavior at the air/water interface were systematically determined by quantitative polarization analysis. The transition dipole of the CN stretching of the SCN- anion is oriented around 44° from the surface normal of the NaSCN aqueous solution surface and remained unchanged with the bulk concentration varying from 1 mol kg-1 to 13 mol kg-1. The free energy of adsorption of SCN- anions at the air/water interface was determined to be -1.53 ± 0.04 kcal mol-1. Furthermore, a new SFG peak positioned at 2080 cm-1 in the ppp polarization combination was observed at the air/15.0 mol kg-1 NaSCN aqueous solution interface for the first time. Concentration-dependent SFG analysis and density functional theory (DFT) calculation further revealed that the SCN- anions form an ion clustering structure at the air/water interface. The subtle and specific Na+ and K+ counter-cation effects on the interfacial structure of the SCN- anions at the aqueous solution interface were also observed, which showed that ion cooperativity plays an important role in affecting the interfacial structure of ions at the air/water interface. The results are expected to yield significant insights into the understanding of the structure of aqueous solution surfaces and the molecular level mechanism of the cationic Hofmeister effect.

Understanding the intramolecular vibrational energy transfer and structural dynamics of anionic ligands in a photo-catalytic CO2 reduction catalyst.

The knowledge of intramolecular vibrational energy redistribution (IVR) and structural dynamics of rhenium photo-catalysts is essential for understanding the mechanism of the photo-catalytic process of CO2 reduction. In this study, the rhenium compound Re(dcbyp)(CO)3NCS (Re-NCS), which served as a model CO2 reduction catalyst, was investigated using two dimensional infrared (2D IR) spectroscopy. The vibrational relaxation dynamics and rotational dynamics of Re-NCS were measured by monitoring both the CO and NCS vibrational modes. The rotational dynamics measurement of the CO vibrational stretch shows a single exponential decay with a time constant of 140 ± 10 ps. In contrast, a bi-exponential decay is needed to describe the rotational dynamics of the NCS stretching mode with time constants of 1.5 ± 0.3 ps and 189 ± 15 ps. The 2D IR experiment indicated that the carbonyl CO vibrational modes in Re-NCS are strongly coupled. Furthermore, the intramolecular vibrational energy transfer between CO and NCS stretching modes was observed and analyzed based on an energy exchange model. The energy down flowing transfer from CN to CO stretching mode was determined using time constants of 50 ps. The relatively slow intramolecular vibrational energy transfer rate suggests that there is a weak coupling between CO and NCS ligands. Further theoretical calculation showed that the coupling strength between CO and CN is relatively weak and is about 5-6 times smaller than the coupling strength between the CO vibrational modes in Re-NCS. The distinct structural dynamics of the NCS ligand in Re-NCS presented in this study should provide a fundamental understanding of the role of an anionic ligand in rhenium photo-catalysts, which is believed to play an important role in the photo-catalytic reduction of CO2.

Molecular structure and adsorption of dimethyl sulfoxide at the air/aqueous solution interface probed by non-resonant second harmonic generation.

In this study, non-resonant second harmonic generation (SHG) was used to investigate the molecular structure and adsorption of DMSO at the air/neat DMSO liquid and air/DMSO aqueous solution interfaces. The molecular orientation of interfacial DMSO as a function of the bulk DMSO concentration was investigated by quantitative polarization SHG analysis. For the air/neat DMSO liquid interface, the transition dipole moment of the S[double bond, length as m-dash]O group of DMSO is oriented 140° from the surface normal, where the S[double bond, length as m-dash]O group of DMSO is estimated to be 30° from the surface plane. The orientation of the S[double bond, length as m-dash]O group of interfacial DMSO is not dependent on the bulk DMSO concentration. Furthermore, the concentration-dependent SHG signal confirmed that the antiparallel double layer structure does not form at the air/DMSO water interface. The free energy of adsorption of DMSO at the air/DMSO aqueous solution interface was determined to be ΔGads = -5.6 ± 0.4 kJ mol-1.

Non-parabolic potential dependence of optical second harmonic generation from the Si(111) electrode/electrolyte interface.

We performed potential dependent second harmonic generation (SHG) measurements on the Si(111) electrolyte interface at different azimuthal angles and for different polarization combinations. When the external potential was biased from the equilibrium potential to the flatband potential (Efb), the SHG intensity decreased linearly with the potential when the azimuthal angle was oriented at 30°. This linearity extends well beyond the linear region of the Mott-Schottky plot as measured traditionally by capacitance measurements. When the external potential was scanned from Efb toward more negative potentials, the response of SHG intensity showed quadratic behavior and can be described by the parabolic model. The non-parabolic potential dependence cannot be explained with the parabolic model proposed from previous literature. Such asymmetric behavior only implied that the interfacial structure of the Si(111) electrode changes from semiconductor to metal with the applied electric potential biased negatively, i.e. with accumulation of electrons in the surface region. The anisotropic contribution from the Si(111) electrode can also significantly affect the SHG response as seen where the minimum of the potential dependent SHG curve shifts away from Efb.

Terahertz vibrational modes of the rigid crystal phase of succinonitrile.

Succinonitrile (N ≡ C-CH2-CH2-C ≡ N), an orientationally disordered molecular plastic crystal at room temperature, exhibits rich phase behavior including a solid-solid phase transition at 238 K. In cooling through this phase transition, the high-temperature rotational disorder of the plastic crystal phase is frozen out, forming a rigid crystal that is both spatially and orientationally ordered. Using temperature-dependent terahertz time-domain spectroscopy, we characterize the vibrational modes of this low-temperature crystalline phase for frequencies from 0.3 to 2.7 THz and temperatures ranging from 20 to 220 K. Vibrational modes are observed at 1.122 and 2.33 THz at 90 K. These modes are assigned by solid-state density functional theory simulations, corresponding respectively to the translation and rotation of the molecules along and about their crystallographic c-axis. In addition, we observe a suppression of the phonon modes as the concentration of dopants, in this case a lithium salt (LiTFSI), increases, indicating the importance of doping-induced disorder in these ionic conductors.

Unveiling the Structural and Dynamic Characteristics of Concentrated LiNO3 Aqueous Solutions through Ultrafast Infrared Spectroscopy and Molecular Dynamics Simulations.

Highly concentrated aqueous electrolytes have attracted a significant amount of attention for their potential applications in lithium-ion batteries. Nevertheless, a comprehensive understanding of the Li+ solvation structure and its migration within electrolyte solutions remains elusive. This study employs linear vibrational spectroscopy, ultrafast infrared spectroscopy, and molecular dynamics (MD) simulations to elucidate the structural dynamics in LiNO3 solutions by using intrinsic and extrinsic vibrational probes. The N-O stretching vibrations of NO3- exhibit a distinct spectral splitting, attributed to its asymmetric interaction with the surrounding solvation structure. Analysis of the vibrational relaxation dynamics of intrinsic and extrinsic probes, in combination with MD simulations, reveals cage-like networks formed through electrostatic interactions between Li+ and NO3-. This microscopic heterogeneity is reflected in the intertwined arrangement of ions and water molecules. Furthermore, both vehicular transport and structural diffusion assisted by solvent rearrangement for Li+ were analyzed, which are closely linked with the bulk concentration.

Dynamics of Formamide-Water Mixtures Investigated by Linear and Nonlinear Infrared Spectroscopy.

Formamide (FA) exhibits complete miscibility with water, offering a simplified model for exploring the solvation dynamics of peptide linkages in biophysical processes. Its liquid state demonstrates a three-dimensional hydrogen bonding network akin to water, reflecting solvent-like behavior. Analyzing the microscopic structure and dynamics of FA-water mixtures is expected to provide crucial insights into hydrogen bonding dynamics─a key aspect of various biophysical phenomena. This study is focused on the dynamics of FA-water mixtures using linear and femtosecond infrared spectroscopies. By using the intrinsic OD stretch and extrinsic probe SCN-, the local vibrational behaviors across various FA-water compositions were systematically investigated. The vibrational relaxation of OD stretch revealed a negligible impact of FA addition on the vibrational lifetime of water molecules, underscoring the mixture's water-like behavior. However, the reorientational dynamics of OD stretch slowed with increasing FA mole fraction (XFA), plateauing beyond XFA > 0.5. This suggests a correlation between OD's reorientational time and the strength of the hydrogen bond network, likely tied to the solution's changing dielectric constant. Conversely, the vibrational relaxation dynamics of SCN- was strongly correlated with XFA, highlighting a competition between water and FA molecules in solvating SCN-. Moreover, a linear relationship between rising viscosity and the prolonged correlation time of SCN-'s slow dynamics indicates that the solution's macroscopic viscosity is dictated by the extended structures formed between FA and water molecules. The relation between the reorientation dynamics of the SCN- and the macroscopic viscosity in aqueous FA-water mixture solutions was analyzed by using the Stokes-Einstein-Debye equations. The direct viscosity-diffusion coupling is observed, which can be attributed to the homogeneous dynamics feature in FA-water mixture solutions. The inclusion of these intrinsic and extrinsic probes not only enhances the comprehensiveness of our analysis but also provides valuable insights into various aspects of the dynamics within the FA-water system. This investigation sheds light on the fundamental dynamics of FA-water mixtures, emphasizing their molecular-level homogeneity in this binary mixture solution.

Relative intermolecular orientation probed via molecular heat transport.

In this work, through investigating a series of liquid, glassy, and crystalline samples with ultrafast multiple-mode 2D IR and IR transient absorption methods, we demonstrated that the signal anisotropy of vibrational relaxation-induced heat effects is determined by both relative molecular orientations and molecular rotations. If the relative molecular orientations are randomized or molecular rotations are fast compared to heat transfer, the signal anisotropy of heat effects is zero. If the relative molecular orientations are anisotropic and the molecular rotations are slow, the signal anisotropy of heat effects can be nonzero, which is determined by the relative orientations of the energy source mode and the heat sensor mode within the same molecule and in different molecules. We also demonstrated that the correlation between the anisotropy value of heat signal and the relative molecular orientations can be quantitatively calculated.

Anion Recognition in Solution: Insights from Thermodynamics and Ultrafast Structural Dynamics.

Anion recognition through noncovalent interactions stands as an emerging field in supramolecular chemistry, exerting a profound influence on the regulation of biological functions. Herein, the thermodynamics of complexation between sodium cyanate (NaOCN) and calix[4]pyrrole was systematically investigated by linear and nonlinear IR spectroscopy, highlighting enthalpy changes as the dominant driving force. The overall orientational relaxation of bound anion can be described by an Arrhenius-type activated process, yielding an activation energy of 15.0 ± 1.0 kJ mol-1. The structural dynamics of contact ion pairs (CIPs) formed between Na+ and OCN- in solution showed a negligible temperature effect, suggesting entropy changes as the principal governing factor. Further analysis revealed that anion recognition in solution is mediated by conformational changes of the receptor and collective rearrangement of hydrogen bond dynamics. This study, framed within the paradigms of thermodynamics and ultrafast structural dynamics, substantially advances our comprehension of the microscopic mechanisms underlying anion recognition in the realm of supramolecular chemistry.

Tracking the Intramolecular Charge Transfer Process of 2,6-Substituted D-A BODIPY Derivatives.

Three 2,6-electron donor-substituted boron dipyrromethene (BODIPY) exhibiting an intramolecular charge transfer (ICT) character with large Stokes shift and moderate fluorescence quantum yields were designed and synthesized. Broadband femtosecond transient absorption (fs-TA) spectroscopy measurements were performed to directly detect the CT state in nonpolar or less polar solvents and the charge separation (CS) state in more polar solvents. A solid foundation for the fs-TA assignment can be found in electrolysis experiments. In addition, the ICT character of the newly designed compounds was investigated by density functional theory (DFT) calculations. Meanwhile, the reference compounds without the donor groups were synthesized, and their photophysical behaviors and ultrafast time-resolved spectra confirmed that no ICT process occurred regardless of the nature of the solvent. This work emphasizes the importance of decorating the BODIPY core with electron-donating substituents at 2,6-positions to efficiently adjust its photofunctional behaviors demonstrating the ICT character. Importantly, the photophysical processes could be easily regulated by changing the solvent with different polarities.

Chain-like Structures Facilitate Li+ Transport in Concentrated Aqueous Electrolytes: Insights from Ultrafast Infrared Spectroscopy and Molecular Dynamics Simulations.

Highly concentrated aqueous electrolytes have attracted attention due to their unique applications in lithium ion batteries (LIBs). However, the solvation structure and transport mechanism of Li+ cations at concentrated concentrations remain largely unexplored. To address this gap in knowledge, we employ ultrafast infrared spectroscopy and molecular dynamics (MD) simulations to reveal the dynamic and spatial structural heterogeneity in aqueous lithium chloride (LiCl) solutions. The coupling between the reorientation dynamics of the extrinsic probe and the macroscopic viscosity in aqueous LiCl solutions was analyzed using the Stokes-Einstein-Debye (SED) equations. MD simulations reveal that the Cl- and Li+ form chain-like structures through electrostatic interactions, supporting the vehicular migration of Li+ through the chain-like structure. The concentration dependent conductivity of the LiCl solution is well reproduced, where Li(H2O)2+ and Li(H2O)3+ are the dominant species that contribute to the conduction of Li+. This study is expected to establish correlations between ion pair structures and macroscopic properties.

Control of n-Phase Distribution in Quasi Two-Dimensional Perovskite for Efficient Blue Light-Emitting Diodes.

Pure-bromide quasi-2D perovskite (PBQ-2DP) promises high-performance light-emitting diodes (LEDs), while a challenge remains on control over its n-phase distribution for bright true-blue emission. Present work addresses the challenge through exploring the passivation molecule of amino acid with reinforced binding energy, which generates narrow n-phase distribution preferentially at n = 3 with true blue emission at 478 nm. Consequently, a peak external quantum efficiency of 5.52% and a record brightness of 512 cd m-2 are achieved on the PBQ-2DP-based true blue PeLED, these both values located among the top in the records of similar devices. We further reveal that the electron-phonon coupling results in the red-shifted emission in the PBQ-2DP film, suggesting that the view of n-phase distribution dominated true-blue emission in PBQ-2DP needs to be revisited, pointing out a guideline of electron-phonon coupling suppression to relieve the strait of realizing true blue or even deep blue emission in the PBQ-2DP film.

Tutorial on the instrumentation of sum frequency generation vibrational spectroscopy: Using a Ti:sapphire based system as an example.

Sum frequency generation vibrational spectroscopy (SFG-VS) is an intrinsically surface-selective vibrational spectroscopic technique based on the second-order nonlinear optical process. Since its birth in the 1980s, SFG-VS has been used to solve interfacial structure and dynamics in a variety of research fields including chemistry, physics, materials sciences, biological sciences, environmental sciences, etc. Better understanding of SFG-VS instrumentation is no doubt an essential step to master this sophisticated technique. To address this need, here we will present a Tutorial with respect to the classification, setup layout, construction, operation, and data processing about SFG-VS. We will focus on the steady state Ti:sapphire based broad bandwidth SFG-VS system and use it as an example. We hope this Tutorial is beneficial for newcomers to the SFG-VS field and for people who are interested in using SFG-VS technique in their research.

Non-negligible Axial Ligand Effect on Electrocatalytic CO2 Reduction with Iron Porphyrin Complexes.

Iron(III) porphyrin complexes have been demonstrated as one of the efficient molecular catalysts for the electrochemical reduction of CO2. However, the role of axial ligands coordinated with a metal center in the complex on the electrochemical CO2 reduction activity has not been fully explored yet. Herein, iron(III) tetraphenylporphyrin thiocyanate (FeTPP-SCN) is synthesized from a commercially available catalyst of FeTPP-Cl by a counteranion exchanging reaction. Cyclic voltammetry measurements showed that the catalytic activity of FeTPP-SCN is noticeably suppressed in the DMF solutions. The structural dynamics of the axial ligand in FeTPP-SCN are further examined by the FTIR and ultrafast IR spectroscopies, where the SCN ligand is employed as the local vibrational probe. Vibrational relaxation measurements showed that the reorientational dynamics of SCN ligands was strongly restricted in DMF solution, suggesting that the subtle electrostatic interaction between the ligands and metal center in the complex can have a non-negligible effect on its catalytic activity.

Exploring the Structure and Complexation Dynamics of Azide Anion Recognition by Calix[4]pyrroles in Solution.

The structure and anion recognition dynamics between calix[4]pyrroles and azide (N3-) anions in the form of its TBA+ and Na+ salts were investigated in dimethyl sulfoxide solutions by Fourier transform infrared (FTIR) spectroscopy and ultrafast IR spectroscopy. Vibrational energy redistribution of the N3- anion in the complex is accelerated through hydrogen bonding interactions with the N-H proton of the receptor. Rotational dynamics of the bound N3- is greatly restricted, demonstrating a distinct countercation effect. The detailed binding modes of N3- with the receptor were further evaluated by the density functional theoretical (DFT) calculations and nuclear magnetic resonance (NMR) spectroscopy. All of these measurements support the notion that the calix[4]pyrroles are capable of capturing the azide anion in solution. However, the calix[4]pyrroles may not necessarily undergo a conformational change to a cone-like geometry when they bind to the azide anion in the solution.

Distinct Hydrogen Bonding Dynamics Underlies the Microheterogeneity in DMF-Water Mixtures.

The hydrogen bonding interaction between the amide functional group and water is fundamental to understanding the liquid-liquid heterogeneity in biological systems. Herein, the structure and dynamics of the N,N-dimethylformamide (DMF)-water mixtures have been investigated by linear and nonlinear IR spectroscopies, using the hydroxyl stretch and extrinsic probe of thiocyanate as local vibrational reporters. According to vibrational relaxation dynamics measurements, the orientational dynamics of water is not directly tied to those of DMF molecules. Wobbling-in-a-cone analysis demonstrates that the water molecules have varying degrees of angular restriction depending on their composition due to the formation of specific water-DMF networks. Because of the preferential solvation by DMF molecules, the rotational dynamics of the extrinsic probe is slowed significantly, and its rotational time constants are correlated to the change of solution viscosity. The unique structural dynamics observed in the DMF-water mixtures is expected to provide important insights into the underlying mechanism of microscopic heterogeneity in binary mixtures.

Structural Dynamics of Short Ligands on the Surface of ZnSe Semiconductor Nanocrystals.

ZnSe semiconductor nanocrystals (NCs) with a size comparable to their Bohr radius are synthesized, and the native capping agents with long hydrocarbon tails are replaced with short thiocyanate (SCN) ligands through a ligand exchange method. The structural dynamics of SCN ligands on the surface of ZnSe NCs in solution is investigated by ultrafast infrared spectroscopy. Vibrational population relaxation of SCN ligands is accelerated due to the specific interaction with the positively charged sites on the surface of NCs. The orientational anisotropy of the bound SCN ligands decayed at a rate much faster than that in the control solution containing Zn2+ cations. From the wobbling-in-the-cone model analysis, we found that the SCN ligand undergoes wobbling orientational diffusion with a relatively large cone semiangle on the surface of ZnSe NCs, and the overall orientational diffusion of bound SCN is found to be strongly dependent on the size of ZnSe NCs.

Self-Assembly of Amphiphilic BODIPY Derivatives on Micropatterned Ionic Liquid Surfaces for Fluorescent Films with Excellent Stability and Sensing Performance.

Fluorescent films have been widely recognized as one of the most powerful tools for trace analyte detection. However, their use has been limited due to the poor photochemical stability of fluorophores at a gas-solid interface and inefficient film mass transfer. Herein, novel fluorescent films were developed through self-assembly of amphiphilic BODIPY derivatives on micropatterned ionic liquid surfaces. Unlike solid-state films, the obtained monolayer films exhibit excellent photochemical stability, similar to that of a solution. Moreover, the interfacial assembly of amphiphilic fluorophores can avoid gas diffusion inside the microdroplets, significantly improving the sensing performance. The 1/1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4) monolayer exhibits high sensitivity, high selectivity, and a fast response to detect diethylchlorophosphate (DCP) vapor. The detection limit was 226 ppt, with a response time to DCP of 2.0 s. Importantly, the 1/[BMIM]BF4 monolayer can be reused for at least 50 cycles with no obvious signal fading. This study is expected to benefit the development of new strategies for designing fluorescence sensing films and lay a solid foundation for the fabrication of multifunctional sensing devices with excellent photochemical stability and sensing performance.