COSMO-RS Exploration of Highly CO2-Selective Hydrogen-Bonded Binary Liquid Absorbents under Humid Conditions: Role of Trace Ionic Species.

It is critical to improve carbon capture efficiency while reducing costs to popularize carbon capture and storage. Considering the green chemistry and engineering objectives, this study theoretically explores the CO2 absorption capacity of 1,533,528 hydrogen-bonded mixtures, i.e., deep eutectic solvents in a broad sense. Exhaustive statistical thermodynamic calculations well explain the experimental reports; it is confirmed that deep eutectic solvents containing ionic compounds have higher CO2 selective absorption capacity than those composed of non-ionic species. Quantitative evaluation of hydrogen-bonding interaction also predicts that the capacity is higher when the ionic compounds work as hydrogen-bonding donors. This is because the trace ionic species weaken the hydrogen-bonding network in the mixtures to improve CO2 physisorption.

Machine Learning-Boosted Design of Ionic Liquids for CO2 Absorption and Experimental Verification.

Efficient CO2 capture is indispensable for achieving a carbon-neutral society while maintaining a high quality of life. Since the discovery that ionic liquids (ILs; room-temperature molten salts) can absorb CO2, various solvents composed of molecular ions have been studied. However, it is challenging to observe the properties of each isolated ion component to control the function of ILs as they are mixtures of ions. Finding the optimal cation-anion combination for the CO2 absorbent from their enormous chemical space had been impossible in a practical sense. This study applied electronic structure informatics to explore ILs with high CO2 solubility from 402,114 IL candidates. The feature variables were determined by a set of cheap quantum chemistry calculations for isolated small-ion fragments, and the importance of molecular geometries and electronic states governing molecular interactions was identified via the wrapper method. As a result, it was clearly shown that the electronic states of ionic species must have essential roles in the CO2 physisorption capacity of ILs. Considering synthetic easiness for the candidates narrowed by the machine learning model, trihexyl(tetradecyl)phosphonium perfluorooctanesulfonate was synthesized. Using a magnetic suspension balance, it was experimentally confirmed that this IL has higher CO2 solubility than trihexyl(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide, which is the previous best IL for CO2 absorption.

On donor-acceptor-bridging intramolecular hydrogen bonds in NIR-TADF molecules.

Following a report that highlights the importance of intramolecular hydrogen bonds for improved NIR-TADF efficiency in CAT-1 [Leng et al., J. Phys Chem. A, 2021, 125, 2905], an intramolecularly doubly hydrogen-bonded base design is investigated and compared to singly and non-bonded derivatives. It is found that the potential to form more intramolecular hydrogen bonds correlates with decreasing internal reorganization energies in most of the designed structures. In addition, our proposed base design facilitates the desired interlocking of charge transfer donor-, linker- and acceptor-planes through steric gauche-interactions to both linker-plane sides, allowing to trap also smaller heterocyclic linkers.

Electronic fluctuation difference between trimethylamine N-oxide and tert-butyl alcohol in water.

Although small organic molecules in cells have been considered important to control the functions of proteins, their electronic fluctuation and the intermolecular interaction, which is physicochemical origin of the molecular functions, under physiological conditions, i.e., dilute aqueous solutions (0.18 mol L-1), has never been clarified due to the lack of observation methods with both accuracy and efficiency. Herein, the time evolutions of the interactions in dilute aqueous trimethylamine N-oxide (TMAO) and tert-butyl alcohol (TBA) solutions were analyzed via ab initio molecular dynamics simulations accelerated with the fragment molecular theory. It has been known that TMAO and TBA have similar structures, but opposite physiological functions to stabilize and destabilize proteins. It was clarified that TMAO induced stable polarization and charge-transfer interactions with water molecules near the hydrophilic group, and water molecules were caught even near the CH3- group. Those should affect protein stabilization. Understanding the solution dynamics will contribute to artificial chaperone design in next generation medicine.

Room-Temperature Phosphorescence Emitters Exhibiting Red to Near-Infrared Emission Derived from Intermolecular Charge-Transfer Triplet States of Naphthalenediimide-Halobenzoate Triad Molecules.

Invited for the cover of this issue is Toshikazu Ono, Yoshio Hisaeda and co-workers at Kyushu University and their collaborators at Ochanomizu University, Chuo University, and Institute for Molecular Science. The image depicts a molecular assembly structure shining like a jewel, glowing in the red-to-near infrared region. Read the full text of the article at 10.1002/chem.202100906.

Room-Temperature Phosphorescence Emitters Exhibiting Red to Near-Infrared Emission Derived from Intermolecular Charge-Transfer Triplet States of Naphthalenediimide-Halobenzoate Triad Molecules.

Room-temperature phosphorescence (RTP) emitters have attracted significant attention. However, purely organic RTP emitters in red to near-infrared region have not been properly investigated. In this study, a series of naphthalenediimide-halobenzoate-linked molecules are synthesized, one of which exhibits efficient RTP properties, showing red to near-infrared emission in solid and aqueous dispersion. Spectroscopic studies and single-crystal X-ray diffraction analysis have shown that the difference in the stacking modes of compounds affects the optical properties, and the formation of intermolecular charge-transfer complexes of naphthalenediimide-halobenzoate moiety results in a bathochromic shift of absorption and RTP properties. The time-dependent density functional theory calculations showed that the formation of charge-transfer triplet states and the external heavy atom effect of the halogen atom enhance the intersystem crossing between excited singlet and triplet states.

Functional Group-Directed Photochemical Reactions of Aromatic Alcohols, Amines, and Thiols Triggered by Excited-State Hydrogen Detachment: Additive-free Oligomerization, Disulfidation, and C(sp2)-H Carboxylation with CO2.

Exploring new types of photochemical reactions is of great interest in the field of synthetic chemistry. Although excited-state hydrogen detachment (ESHD) represents a promising prospective template for additive-free photochemical reactions, applications of ESHD in a synthetic context remains scarce. Herein, we demonstrate the expansion of this photochemical reaction toward oligomerization, disulfidation, and regioselective C(sp2)-H carboxylation of aromatic alcohols, thiols, and amines. In the absence of any radical initiators in tetrahydrofuran upon irradiation with UV light (λ = 280 or 300 nm) under an atmosphere of N2 or CO2, thiols and catechol afforded disulfides and oligomers, respectively, as main products. Especially, the photochemical disulfidation proceeded highly selectively with the NMR and quantum yields of up to 69 and 0.46%, respectively. In stark contrast, the photolysis of phenylenediamines and aminophenols results in photocarboxylation in the presence of CO2 (1 atm). p-Aminophenol was quantitatively carboxylated by photolysis for 17 h with a quantum yield of 0.45%. Furthermore, the photocarboxylation of phenylenediamines and aminophenols proceeds in a highly selective fashion on the aromatic C(sp2)-H bond next to a functional group, which is directed by the site-selective ESHD of the functional groups for the formation of aminyl and hydroxyl radicals.

Cyclic Heterometallic Interactions formed from a Flexible Tripeptide Complex Showing Effective Antiferromagnetic Spin Coupling.

Developing tunable motifs for heterometallic interactions should be beneficial for fabricating functional materials based on cooperative electronic communications between metal centers. Reported here is the efficient formation of cyclic heterometallic interactions from a complex containing an artificial tripeptide with metal binding sites on its main chain and side chains. X-ray structural analysis and X-ray absorption spectroscopy revealed that the cyclic metal-metal arrangements arise from the amide groups connecting four square-planar CuII centers and four octahedral NiII centers in a cyclic manner. UV/Vis spectral studies suggested that this efficient formation was achieved by the selective formation of the square-planar CuII centers and a crystallization process. Magnetic measurements using SQUID clarified that the cyclic complex represented the S=2 spin state at low temperatures due to effective antiferromagnetic interactions between the NiII and CuII centers.

Development of Helical Aromatic Amide Foldamers with a Diphenylacetylene Backbone.

We designed and synthesized aromatic polyamides with a diphenylacetylene backbone, α-DPA and ß-DPA, bearing (S)-α- and (S)-ß-methyl-substituted triethyleneglycol (TEG) side chains, respectively, and examined their conformations in solution. Both polymers exhibit strong, solvent polarity-dependent circular dichroism spectra, which indicated that they take helical conformations in low-polarity solvents. The spectra were mirror images, depending on the chiral position of the side chains. Thus, the polyamide α-DPA bearing (S)-α-methyl-substituted TEG groups takes a left-handed helical conformation, while the polyamide ß-DPA with (S)-ß-methyl-substituted TEG groups takes a right-handed helical conformation. The difference in the screw sense of α-DPA and ß-DPA would be caused by the steric interaction between the main chain and the side chain, as observed in poly(p-benzamide) possessing (S)-ß-methyl-substituted TEG side chains (ß-PA) because the large cavity of the helical structure of DPA would disturb the solvophobically induced helical folding. Detailed conformational analyses of the oligoamides 6-12 with ß-methyl-substituted TEG groups were conducted. Theoretical calculations indicated that the oligoamides with ß-methyl-substituted TEG groups exist in a helical conformation with a cavity of 7 Å in diameter. The 1H NMR spectra of the oligomers revealed interactions with small anions such as chloride and acetate anions and with pyridinium cations.

Synthesis, X-ray structure, photophysical properties, and theoretical studies of six-membered cyclometalated iridium(iii) complexes: revisiting Ir(pnbi)2(acac).

We have determined the X-ray structure of Ir(pnbi)2(acac) (pnbi = 2-phenanthren-9-yl-1-phenyl-1H-benzimidazole; acac = acetylacetonate), which exhibits a six-membered metallocycle around the Ir center. This result stands in sharp contrast to previously postulated structures of Ir(pnbi)2(acac), which assumed a five-membered metallocycle. In this paper, we focus on the relative stability of five- and six-membered Ir(C^N) ring structures. DFT calculations of the total energies of Ir-(C^N) complexes indicated that six-membered structures are more stable when bulky substituents are present in the benzimidazole unit. When the phenanthrene group of pnbi was replaced with a naphthalene moiety, DFT calculations predicted that five-membered cycles are more stable than six-membered rings, which was confirmed experimentally by a single-crystal X-ray diffraction analysis. The steric bulk of the phenanthrene-containing polyaromatic ring ligand thus induces greater interligand repulsion between the two ligands, which plays an important role in determining the cyclometalation route. The Ir complexes examined in this study exhibit red emission (λem ≈ 660 nm) with relatively low quantum yields.

Applicability of Effective Fragment Potential Version 2-Molecular Dynamics (EFP2-MD) Simulations for Predicting Dynamic Liquid Properties Including the Supercritical Fluid Phase.

Effective fragment potential version 2-molecular dynamics (EFP2-MD) simulations, where the EFP2 is a polarizable force field based on ab initio electronic structure calculations, were applied to predict the static and dynamic liquid properties of compressed liquid NH3. By analyzing the temperature dependence of the radial distribution function, the autocorrelation functions of velocity ( Cv( t)) and reorientation ( Cr( t)), and the self-diffusion constant, we clarified that the ab initio EFP2 force field can effectively describe the properties of compressed liquids. These descriptions can be performed with at least semiquantitative accuracy and at a sufficiently low computational cost. In the EFP2-MD protocol, no force field training is required. This training is mandatory when simulating liquid properties with classical MD techniques (especially in extreme conditions with high pressures and temperatures). EFP2-MD is a promising technique for predicting the physicochemical properties of novel functional compressed liquids, including supercritical fluid phase properties.

Synthesis and Conformational Analysis of Alternately N-Alkylated Aromatic Amide Oligomers.

Alternately N-alkylated aromatic amides such as 1-3 bearing various side chains were designed and synthesized as novel helical foldamers. The CD spectra of oligomers with chiral side chains showed a positive Cotton effect, which indicates that these oligomers take helical conformations in solution. The CD intensity gradually increased with increasing chain length, and pentamer 3d showed remarkably strong CD signals in chloroform. The absorption maxima of the UV spectra were increasingly red shifted with increasing chain length, in contrast to the case of poly( p- N-alkylbenzamide)s. Structure optimization of the oligomers based on the crystal structure of 1a as the monomer unit supported the formation of helical structure with a large cavity and also suggested intramolecular hydrogen bond formation between secondary amides. The results of calculation were consistent with the observed spectroscopic features.

Stereoselective interactions as manifested by vibrational circular dichroism spectra: the interplay between chiral metal complexes co-adsorbed in a montmorillonite clay.

Vibrational circular dichroism (VCD) spectroscopy was applied to study intermolecular interactions on the surface of a clay mineral. A montmorillonite clay loaded with two kinds of chiral molecules was prepared. Firstly a cationic ruthenium(ii) complex, Δ- or Λ-[Ru(phen)3]2+ (phen = 1,10-phenanthroline), was ion-exchanged into sodium montmorillonite (denoted as [Ru(phen)3]2+/mont). Thereafter a neutral metal(iii) complex, Δ- or Λ-[M(acac)3] (acac = acetylacetonato; M = Co and Cr), was adsorbed spontaneously, when the complex was added to an aqueous dispersion of [Ru(phen)3]2+/mont (denoted as [M(acac)3]/[Ru(phen)3]2+/mont). VCD measurements were performed on a KBr disk containing ca. 1 wt% of solid [M(acac)3]/[Ru(phen)3]2+/mont. Both of the chiral components gave clear VCD peaks in the wavelength region of 1200-1800 cm-1. Attention was focussed on the spectral differences between the following two samples: the one containing a pair of co-adsorbed chelates with the same chirality (i.e. Λ-[M(acac)3]/Λ-[Ru(phen)3]2+/mont or Δ-[M(acac)3]/Δ-[Ru(phen)3]2+/mont) and the other containing a pair of co-adsorbed chelates with the opposite chirality (i.e. Δ-[M(acac)3]/Λ-[Ru(phen)3]2+/mont or Λ-[M(acac)3]/Δ-[Ru(phen)3]2+/mont). Notably a new peak shoulder appeared and the relative peak intensity of the couplet peaks varied, depending on the chirality relation between the co-existing complexes. With the help of theoretical calculations, these results were rationalized in terms of the stereoselective intermolecular interactions.

Conformational Properties of Aromatic Oligoamides Bearing Pyrrole Rings.

N-Alkylbenzanilides generally exist in cis conformation both in the crystalline state and in various solvents, and this cis conformational preference can be utilized to construct dynamic helical oligoamides. Here, we synthesized the pyrrole-containing amides 2-5 and their oligomers 6-8 and examined their conformations in the crystalline state and in solution. All the N-methylated amides showed cis conformational preference in solution, but the ratio of the cis isomer was decreased when the amide bond was attached at the 4-position of the pyrrole ring, probably because the destabilization of the trans conformer due to electronic repulsion between the pyrrole π electrons and the amide carbonyl lone-pair electrons is reduced due to the small torsion angle between the 5-membered N-pyrrole and the amide bond. In the crystalline state, N-methylated amides showed cis structure, except for compound 5, and cis conformational preference was observed for the pyrrole amides. The CD spectra of oligoamides 15-18 bearing chiral N-substituents were consistent with the presence of dynamic and well-defined chiral foldamers, which were structurally distinct from N-alkylated poly( p-benzamide)s 1.

Origin of high oxygen reduction reaction activity of Pt12 and strategy to obtain better catalyst using sub-nanosized Pt-alloy clusters.

In the present study, methods to enhance the oxygen reduction reaction (ORR) activity of sub-nanosized Pt clusters were investigated in a theoretical manner. Using ab initio molecular dynamics and Monte Carlo simulations based on density functional theory, we have succeeded in determining the origin of the superior ORR activity of Pt12 compared to that of Pt13. That is, it was clarified that the electronic structure of Pt12 fluctuates to a greater extent compared to that of Pt13, which leads to stronger resistance against catalyst poisoning by O/OH. Based on this conclusion, a set of sub-nanosized Pt-alloy clusters was also explored to find catalysts with better ORR activities and lower financial costs. It was suggested that Ga4Pt8, Ge4Pt8, and Sn4Pt8 would be good candidates for ORR catalysts.

Theoretical study on vibrational circular dichroism spectra of tris(acetylacetonato)metal(III) complexes: anharmonic effects and low-lying excited states.

The open-shell density functional theory calculations with M06 exchange-correlation functional and all-electron Douglas-Kroll second order scalar relativistic correction were performed to interpret the vibrational circular dichroism (VCD) spectra of four kinds of tris(acetylacetonato)metal(III), [M(III)(acac)(3)] (acac = acetylacetonato, M = Ru, Cr, Co, and Rh). It was deduced that the experimental spectra were well reproduced by the calculation with harmonic approximation in case of [Co(III)(acac)(3)] (d(6); S = 0), [Rh(III)(acac)(3)] (d(6); S = 0), and [Ru(III)(acac)(3)] (d(5); S = 1/2). In case of [Cr(III)(acac)(3)] (d(3); S = 3/2), anharmonic effects should be taken into account to predict the accurate vibrational frequencies of closely located modes. Time-dependent density functional theory calculations were performed to estimate the contribution of excited states in the VCD spectra. As a consequence, the presence of the low-lying excited states was predicted for [Ru(III)(acac)(3)] alone, which agreed with the experimental observation.

A theoretical study of the physicochemical mechanisms associated with DNA recognition modulation in artificial zinc-finger proteins.

The DNA-binding ability of the zinc-finger (ZF) protein and the modulation of its affinity to DNA through amino acid mutations were theoretically investigated. Classical molecular dynamics and energy decomposition analysis based on large-scale ab initio fragment molecular orbital calculations were used to obtain the DNA binding affinities of wild-type and three mutant ZFs. Calculated binding free energies qualitatively well explained the DNA binding affinity modulation experimentally observed by Dhanasekaran et al. [Dhanasekaran, M.; et al., Biochemistry 2007, 46, 7506-7513]. It had been considered that only the α-helix domain in the ZF plays an important role in DNA recognition; however, our results clearly show that the N-terminal regions, BR1 and BR2, also play important roles in DNA recognition.

Application of a novel combination of near-infrared spectroscopy and a humidity-controlled 96-well plate to the characterization of the polymorphism of imidafenacin.

OBJECTIVES: This study aimed to apply a currently available chemometric near-infrared spectroscopy technique to the characterization of the polymorphic properties of drug candidates. The technique requires only small quantities of samples and is therefore applicable to drugs in the early stages of development. METHODS: The combination of near-infrared spectroscopy and a patented 96-well plate divided into 32 individual, humidity-controlled, three-well compartments was used in the characterization of a hygroscopic drug, imidafenacin, which has two polymorphs and one pseudo-polymorph. Characterization was also conducted with powder X-ray diffraction and thermal analysis. The results were compared with those from routinely used conventional analyses. KEY FINDINGS: Both the microanalysis and conventional analysis successfully characterised the substance (transformation and relative stability among the two polymorphs and a pseudo-polymorph) depending on the storage conditions. Near-infrared spectroscopic analyses utilizing a humidity-controlled 96-well plate required only small amounts of the sample for characterization under the various conditions of relative humidity. CONCLUSIONS: Near-infrared microanalysis can be applied to polymorphic studies of small quantities of a drug candidate. The results also suggest that the method will predict the behaviors of a hygroscopic candidate in solid pharmaceutical preparations at the early stages of drug development.

Model core potential and all-electron studies of molecules containing rare gas atoms.

Molecules HRgF (Rg = Ar, Kr, Xe, Rn) were studied at levels of theory that included electron correlation, taking relativistic effects into account either by using the recently developed parametrization of the extended model core potentials and basis sets or by using the Douglas-Kroll method with all-electron basis sets. Charge distributions were calculated according to Mulliken, Lowdin, and natural bond orbital methods of population analysis and the results of these methods were compared, confirming that bonding in these molecules corresponds to interaction between the fluoride anion and the RgH(+) moiety. In contrast to previously reported results, the present calculations show that the radon compound, HRnF, is more stable than compounds of the lighter congeners. Trends in the first ionization energies, bond lengths, energies of formation and decomposition, and harmonic vibrational frequencies were discussed and found to be consistent with the periodic trends of the atomic properties of the rare gas atoms.

Theoretical quest for photoconversion molecules having opposite directions of the electric dipole moment in S0 and S1 states.

Ab initio calculations at the level of CASPT2 with Dunning's correlation consistent cc-pVXZ (X=D, T, Q) basis sets have been carried out for pyrimidine, quinoxaline, phthalazine, and their substituted compounds to find candidates that show a change in the direction of the electric dipole moment for the S(0)-->S(1) transition. The present calculations reveal that 6,7-difluorophthalazine and 6,7-dichlorophthalazine are strong candidates having a large and clear change in the direction of the electric dipole moment on the S(0)-->S(1) transition.