論文 - 林　聡子

Extremely stable system of 1-haloselanyl-anthraquinones: Experimental and theoretical investigations

Naoki Ogawa, Nobuhiro Suzuki, Yoshifumi Katsura, Mao Minoura, Waro Nakanishi, Satoko Hayashi (担当区分： 責任著者 )

Dalton Transactions   53   10099 - 10112   2024年05月  [査読有り]

Origin of 13C NMR chemical shifts elucidated based on molecular orbital theory: paramagnetic contributions from orbital-to-orbital transitions for the pre-α, α, β, α-X, β-X and ipso-X effects, along with effects from characteristic bonds and groups.

Waro Nakanishi, Satoko Hayashi, Keigo Matsuzaki (担当区分： 責任著者 )

RSC advances ( the Royal Society of Chemistry )  15 ( 3 ) 1924 - 1940   2025年01月  [査読有り]

　概要を見る

13C NMR chemical shifts (δ(C)) were analysed via MO theory, together with the origin, using σ d(C), σ p(C) and σ t(C), where C4- was selected as the standard for the analysis since σ p(C: C4-) = 0 ppm. An excellent relationship was observed between σ d(C) and the charges on C for (C4+, C2+, C0, C2- and C4-) and (C4-, CH2 2-, CH3 - and CH4). However, such a relationship was not observed for the carbon species other than those above. The occupied-to-unoccupied orbital (ψ i →ψ a ) transitions were mainly employed for the analysis. The origin was explained by the pre-α, α, β, α-X, β-X and ipso-X effects. The pre-α effect of an approximately 20 ppm downfield shift is theoretically predicted, and the observed α and β effects of approximately 10-15 ppm downfield shifts are well reproduced by the calculations, as are the variations in the α-X, β-X and ipso-X effects. Large downfield shifts caused by the formation of ethene (∼120 ppm), ethyne (∼60 ppm) and benzene (∼126 ppm) from ethane and carbonyl (∼146 ppm) and carboxyl (∼110 ppm) groups from CH3OH are also reproduced well by the calculations. The analysis and illustration of σ p(C) through the ψ i →ψ a transitions enables us to visualize the effects and to understand the δ(C) values for the C atoms in the specific positions of the species. The occupied-to-occupied orbital (ψ i →ψ j ) transitions are also examined. The theoretical investigations reproduce the observed results of δ(C). The origin for δ(C) and the mechanism are visualized, which allows us to image the process in principle. The role of C in the specific position of a compound in question can be more easily understood, which will aid in the development of highly functional compounds based on NMR.

DOI

Origin of ¹⁷O NMR chemical shifts based on molecular orbital theory: paramagnetic terms of the pre-α, α and β effects from orbital-to-orbital transitions, along with the effects from vinyl, carbonyl and carboxyl groups

Keigo Matsuzaki, Satoko Hayashi, Waro Nakanishi (担当区分： 責任著者 )

RSC Advances ( Royal Society of Chemistry (RSC) )  14 ( 20 ) 14340 - 14356   2024年04月  [査読有り]

　概要を見る

The plain rules founded in theory, other than the empirical rules, were established for the origin of δ(O) to understand the mechanisms to arise ¹⁷O NMR chemical shifts, based on the MO theory, where the pre-α, α and β effects were employed for the purpose, which were analyzed mainly by σ^p(O).

DOI

Intrinsic dynamic and static natures of ^APn--X⁺--^BPn σ(3c–4e) type interactions (^APn = ^BPn = N, P, As and Sb; X = H, F, Cl, Br and I) in bicyclo[3.3.3] and bicyclo[4.4.4] systems and their behaviour, elucidated with QTAIM dual functional analysis

Taro Nishide, Waro Nakanishi, Satoko Hayashi (担当区分： 責任著者 )

RSC Advances ( Royal Society of Chemistry (RSC) )  14 ( 8 ) 5675 - 5689   2024年01月  [査読有り]

　概要を見る

Natures of the symmetric and nonsymmetric Pn⋯X⁺⋯Pn σ(3c–4e) type interactions (Pn = N, P, As and Sb; X = H, F, Cl, Br and I) in bicyclo[3.3.3] and [4.4.4] systems are elucidated, after clarifying the stability, where X⁺ incorporated in the cage.

DOI

Dynamic and Static Nature of XH-∗-π and YX-∗-π (X = F, Cl, Br, and I; Y = X and F) in the Distorted π-System of Corannulene Elucidated with QTAIM Dual Functional Analysis

Satoko Hayashi, Takahiro Kato, Yuji Sugibayashi, Waro Nakanishi (担当区分： 筆頭著者,　責任著者 )

Molecules ( MDPI AG )  28 ( 10 ) 4219 - 4219   2023年05月  [査読有り]

　概要を見る

The dynamic and static nature of the XH-∗-π and YX-∗-π (X = F, Cl, Br, and I; Y = X and F) interactions in the distorted π-system of corannulene (π(C20H10)) is elucidated with a QTAIM dual functional analysis (QTAIM-DFA), where asterisks emphasize the presence of bond critical points (BCPs) on the interactions. The static and dynamic nature originates from the data of the fully optimized and perturbed structures, respectively, in QTAIM-DFA. On the convex side, H in F–H-∗-π(C20H10) and each X in Y–X-∗-π(C20H10) join to C of the central five-membered ring in π(C20H10) through a bond path (BP), while each H in X–H-∗-π(C20H10) does so to the midpoint of C=C in the central five-membered ring for X = Cl, Br, or I. On the concave side, each X in F–X-∗-π(C20H10) also joins to C of the central five-membered ring with a BP for X = H, Cl, Br, and I; however, the interactions in other adducts are more complex than those on the convex side. Both H and X in X–H-∗-π(C20H10) (X = Cl and Br) and both Fs in F–F-∗-π(C20H10) connect to the three C atoms in each central five-membered ring (with three BPs). Two, three, and five BPs were detected for the Cl–Cl, I–H, Br–Br, and I–I adducts, where some BPs do not stay on the central five-membered ring in π(C20H10). The interactions are predicted to have a vdW to CT-MC nature. The interactions on the concave side seem weaker than those on the convex side for X–H-∗-π(C20H10), whereas the inverse trend is observed for Y–X-∗-π(C20H10) as a whole. The nature of the interactions in the π(C20H10) adducts of the convex and concave sides is examined in more detail, employing the adducts with X–H and F–X placed on their molecular axis together with the π(C24H12) and π(C6H6) adducts.

DOI

Synthesis, structures and reactions of acylsulfenyl iodides with theoretical investigations

Shinzi Kato, Masahiro Kimura, Yukio Komatsu, Kenji Miyagawa, Masaru Ishida, Masahiro Ebihara, Osamu Niyomura, Waro Nakanishi, Satoko Hayashi (担当区分： 責任著者 )

RSC Advances ( Royal Society of Chemistry (RSC) )  13 ( 18 ) 12035 - 12049   2023年04月  [査読有り]

　概要を見る

A series of acylsulfenyl iodides (RCOSI) were synthesized by the reactions of carbothioic acid group 11–16 element derivatives with iodine or N-iodosuccinimides in moderate to good yields.

DOI

Inverse Versus Normal Behavior of Interactions, Elucidated Based on the Dynamic Nature with QTAIM Dual-Functional Analysis

Waro Nakanishi, Satoko Hayashi, Ryosuke Imanaka, Taro Nishide, Eiichiro Tanaka, Hikaru Matsuoka (担当区分： 最終著者,　責任著者 )

International Journal of Molecular Sciences ( MDPI AG )  24 ( 3 ) 2798 - 2798   2023年02月  [査読有り]  [招待有り]

　概要を見る

In QTAIM dual-functional analysis, Hb(rc) is plotted versus Hb(rc) − Vb(rc)/2 for the interactions, where Hb(rc) and Vb(rc) are the total electron energy densities and potential energy densities, respectively, at the bond critical points (BCPs) on the interactions in question. The plots are analyzed by the polar (R, θ) coordinate representation for the data from the fully optimized structures, while those from the perturbed structures around the fully optimized structures are analyzed by (θp, κp). θp corresponds to the tangent line of the plot, and κp is the curvature; θ and θp are measured from the y-axis and y-direction, respectively. The normal and inverse behavior of interactions is proposed for the cases of θp > θ and θp < θ, respectively. The origin and the mechanism for the behavior are elucidated. Interactions with θp < θ are typically found, although seldom for [F–I-∗-F]−, [MeS-∗-TeMe]2+, [HS-∗-TeH]2+ and CF3SO2N-∗-IMe, where the asterisks emphasize the existence of BCPs in the interactions and where [Cl–Cl-∗-Cl]− and CF3SO2N-∗-BrMe were employed as the reference of θp > θ. The inverse behavior of the interactions is demonstrated to arise when Hb(rc) − Vb(rc)/2 and when the corresponding Gb(rc), the kinetic energy densities at BCPs, does not show normal behavior.

DOI

Proposal of pseudo-intrinsic dynamic nature of interactions: simple methods to generate the perturbed structures and to analyze for the prediction of the nature of high reliability, with the applications

Satoko Hayashi, Taro Nishide, Hikaru Matsuoka, Ryosuke Imanaka, Waro Nakanishi (担当区分： 筆頭著者,　最終著者,　責任著者 )

Arkivoc ( ARKAT USA, Inc. )  2023 ( 5 ) 93 - 116   2022年12月  [査読有り]  [招待有り]

DOI

Intrinsic Dynamic and Static Nature of π---π Interactions in Fused Benzene-Type Helicenes and Dimers, Elucidated with QTAIM Dual Functional Analysis

Taro Nishide, Satoko Hayashi (担当区分： 責任著者 )

Nanomaterials ( MDPI )  12 ( 3 ) 321-1 - 321-19   2022年02月  [査読有り]  [招待有り]

　概要を見る

The intrinsic dynamic and static nature of the pi center dot center dot center dot pi interactions between the phenyl groups in proximity of helicenes 3-12 are elucidated with the quantum theory of atoms-in-molecules dual functional analysis (QTAIM-DFA). The pi center dot center dot center dot pi interactions appear in C-*-C, H-*-H, and C-*-H, with the asterisks indicating the existence of bond critical points (BCPs) on the interactions. The interactions of 3-12 are all predicted to have a p-CS/vdW nature (vdW nature of the pure closed-shell interaction), except for C-2(bay)-*-C-7(bay) of 10, which has a p-CS/t-HBnc nature (typical-HBs with no covalency). (See the text for definition of the numbers of C and the bay and cape areas). The natures of the interactions are similarly elucidated between the components of helicene dimers 6:6 and 7:7 with QTAIM-DFA, which have a p-CS/vdW nature. The characteristic electronic structures of helicenes are clarified through the natures predicted with QTAIM-DFA. Some bond paths (BPs) in helicenes appeared or disappeared, depending on the calculation methods. The static nature of C-cape-*-C-cape is very similar to that of C-bay-*-C-bay in 9-12, whereas the dynamic nature of C-cape-*-C-cape appears to be very different from that of C-bay-*-C-bay. The results will be a guide to design the helicene-containing materials of high functionality.

DOI

Intrinsic Dynamic and Static Nature of Halogen Bonding in Neutral Polybromine Clusters, with the Structural Feature Elucidated by QTAIM Dual-Functional Analysis and MO Calculations

Satoko Hayashi, Taro Nishide, Eiichiro Tanaka, Waro Nakanishi (担当区分： 筆頭著者,　責任著者 )

Molecules ( MDPI AG )  26 ( 10 ) 2936 - 2936   2021年05月  [査読有り]

　概要を見る

The intrinsic dynamic and static nature of noncovalent Br-∗-Br interactions in neutral polybromine clusters is elucidated for Br4–Br12, applying QTAIM dual-functional analysis (QTAIM-DFA). The asterisk (∗) emphasizes the existence of the bond critical point (BCP) on the interaction in question. Data from the fully optimized structures correspond to the static nature of the interactions. The intrinsic dynamic nature originates from those of the perturbed structures generated using the coordinates derived from the compliance constants for the interactions and the fully optimized structures. The noncovalent Br-∗-Br interactions in the L-shaped clusters of the Cs symmetry are predicted to have the typical hydrogen bond nature without covalency, although the first ones in the sequences have the vdW nature. The L-shaped clusters are stabilized by the n(Br)→σ*(Br–Br) interactions. The compliance constants for the corresponding noncovalent interactions are strongly correlated to the E(2) values based on NBO. Indeed, the MO energies seem not to contribute to stabilizing Br4 (C2h) and Br4 (D2d), but the core potentials stabilize them, relative to the case of 2Br2; this is possibly due to the reduced nuclear–electron distances, on average, for the dimers.

DOI

Linear Multiselenium Interactions in Dicationic Oligomers of 1,5‐(Diselena)canes: Behavior of σ( mc^c‐ne^e) (6≤ mc ≤16) Elucidated with QTAIM Dual Functional Analysis

Satoko Hayashi, Taro Nishide, Kengo Nagata, Waro Nakanishi (担当区分： 筆頭著者,　責任著者 )

ChemistryOpen ( Wiley )  10   656 - 665   2021年05月  [査読有り]

DOI

Synthesis and Characterization of Monomeric Hexacoordinated Chalcogenonium Salts Bearing 2-(2-Pyridyl)phenyl Ligands

Soichi Sato, Akihisa Ooizumi, Masato Sakabe, Koh Funahashi, Wataru Fujita, Satoko Hayashi, Waro Nakanishi (担当区分： 責任著者 )

Bulletin of the Chemical Society of Japan ( The Chemical Society of Japan )  94 ( 4 ) 1192 - 1200   2021年04月  [査読有り]

DOI

Dynamic and Static Nature of Br4 σ(4c–6e) and Se2Br5 σ(7c–10e) in the Selenanthrene System and Related Species Elucidated by QTAIM Dual Functional Analysis with QC Calculations

Satoko Hayashi, Taro Nishide, Waro Nakanishi (担当区分： 筆頭著者 )

Bioinorganic Chemistry and Applications ( Hindawi Limited )  2020   2901439-1 - 14   2020年07月  [査読有り]

　概要を見る

The nature of Br₄<italic>σ</italic>(4c–6e) of the ^BBr-∗-^ABr-∗-^ABr-∗-^BBr form is elucidated for SeC₁₂H₈(Br)Se<bold>Br---Br-Br---Br</bold>Se(Br)C₁₂H₈Se, the selenanthrene system, and the models with QTAIM dual functional analysis (QTAIM-DFA). Asterisks (∗) are employed to emphasize the existence of bond critical points on the interactions in question. Data from the fully optimized structure correspond to the static nature of interactions. In our treatment, data from the perturbed structures, around the fully optimized structure, are employed for the analysis, in addition to those from the fully optimized one, which represent the dynamic nature of interactions. The ^ABr-∗-^ABr and ^ABr-∗-^BBr interactions are predicted to have the CT-TBP (trigonal bipyramidal adduct formation through charge transfer) nature and the typical hydrogen bond nature, respectively. The nature of Se₂Br₅<italic>σ</italic>(7c–10e) is also clarified typically, employing an anionic model of [<bold>Br-Se</bold>(C₄H₄Se)<bold>-Br---Br---Br-Se</bold>(C₄H₄Se)<bold>-Br</bold>]⁻, the 1,4-diselenin system, rather than (BrSeC₁₂H₈)<bold>Br---Se---Br</bold>-<bold>Br---Br-Se</bold>(C₁₂H₈Se)<bold>-Br</bold>, the selenanthrene system.

DOI

Intrinsic dynamic and static nature of each HB in the multi-HBs between nucleobase pairs and its behavior, elucidated with QTAIM dual functional analysis and QC calculations

Waro Nakanishi, Satoko Hayashi, Taro Nishide (担当区分： 責任著者 )

RSC Advances ( Royal Society of Chemistry (RSC) )  10 ( 41 ) 24730 - 24742   2020年06月  [査読有り]

　概要を見る

<p>Each HB in nucleobase pairs (Nu–Nu′) has the nature close to that of a molecular complex, for example. Energies for the formation of Nu–Nu′ are linearly correlated with the summarized values of the compliance constant of each HB in Nu–Nu′.</p>

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The nature of G⋯E–Y σ(3c–4e) in o-MenGCH2C6H4EY (MenG = Me2N and MeE; E = O, S, Se and Te; Y = F, Cl, Br, EMe and Me) with contributions from CT and compliance constants in noncovalent G⋯E interactions

Satoko Hayashi, Taro Nishide, Waro Nakanishi, Luca Sancineto, Claudio Santi (担当区分： 筆頭著者 )

RSC Advances ( Royal Society of Chemistry (RSC) )  9 ( 67 ) 39435 - 39446   2019年11月  [査読有り]

　概要を見る

<p>The nature of E⋯E′ in 1-RECH₂-2-R′E′C₆H₄ (E/E′ = O, S, Se and Te) is clarified with QTAIM approach and NBO analysis, after structural determinations.</p>

DOI

Dynamic and static nature of activated interactions in transition states as elucidated by quantum theory of atoms-in-molecules dual functional analysis: A case of ligand exchange at the N of sulfonylimino-λ3-bromanes

Waro Nakanishi, Satoko Hayashi, Taro Nishide, Shota Otsuki

Int. J. Quantum Chem.   2019   e26073-1 - e26073-14   2019年11月  [査読有り]

Nature of the E⋯E′ interactions (E, E′ = O, S, Se, and Te) at naphthalene 1,8-positions with fine details of the structures: Experimental and theoretical investigations

Satoko Hayashi, Manabu Uegaito, Taro Nishide, Eiichiro Tanaka, Waro Nakanishi, Takahiro Sasamori, Norihiro Tokitoh, Mao Minoura (担当区分： 筆頭著者 )

New Journal of Chemistry ( Royal Society of Chemistry (RSC) )  43 ( 36 ) 14224 - 14237   2019年08月  [査読有り]

　概要を見る

© 2019 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. The intrinsic dynamic and static natures of the E⋯E′ interactions at the 1,8-positions of 1-(MeE)-8-(MeE′)C10H6 [1a-1f (E ≠ E′) and 1g-1j (E = E′)] were elucidated with QTAIM-DFA, after structural determination of 1-(PhE)-8-(PhE′)C10H6 (3a-3f), where (E, E′: x) = (O, S: A), (O, Se: b), (O, Te: c), (S, Se: d), (S, Te: e), (Se, Te: f), (O, O: g), (S, S: h), (Se, Se: i) and (Te, Te: j) (χE ≥ χE′). While the AB structures are confirmed for 3a, 3b and 3d-3f, which consist of the np(E)⋯σ∗(E′-CPh) interactions, the structure was BB for 3c, where the E-CR/E′-CR (R = Ph) bond is perpendicular to the naphthyl plane in A and it is placed on the plane in B. While the AB structures are determined by the p(E)-π(Ph) conjugations, the BB structure is by the crystal packing effect. The BA structure with np(E′)⋯σ∗(E-CPh) was not detected. While the nature of a typical hydrogen bond with covalency was predicted for BB, AA and BA, with the CT-MC (molecular complex formation through charge transfer) nature for AB in 1e and 1f (R = Me for E-CR/E′-CR), the CT-MC nature was predicted for all conformers of 1j, for example. NBO analysis for 1a-1f revealed that the acceptor orbitals contribute much more than the donor orbitals and the order is σ∗(O-CMe: &lt;0.5 kcal mol-1) ≪ σ∗(S-CMe: ≈5 kcal mol-1) ≪ σ∗(Se-CMe: ≈10 kcal mol-1) ≪ σ∗(Te-CMe: ≈16 kcal mol-1) for np(S), np(Se) and np(Te). The E(2) values proportionally correlate to Cii-1 for AB and/or BA of 1a-1j, if analyzed separately for σ∗(S-C), σ∗(Se-C) and σ∗(Te-C).

DOI

Effects from Basis Sets and Levels of Calculations on the Nature of Interactions Predicted by QTAIM Dual Functional Analysis with QTAIM Functions

Satoko Hayashi, Taro Nishide, Kazuki Ueda, Koki Hayama, Waro Nakanishi (担当区分： 筆頭著者 )

ChemistrySelect ( Wiley )  4 ( 20 ) 6198 - 6208   2019年05月  [査読有り]

DOI

Nature of intramolecular O–H⋯π interactions as elucidated by QTAIM dual functional analysis with QC calculations

Satoko Hayashi, Taro Nishide, Waro Nakanishi (担当区分： 筆頭著者 )

RSC Advances ( Royal Society of Chemistry (RSC) )  9 ( 27 ) 15521 - 15530   2019年05月  [査読有り]

　概要を見る

<p>Intramolecular OH–*–C(π), O–*–C(π) and O–*–H(π) interactions are detected as having a vdW nature, which is typical of an HB with no covalency.</p>

DOI

Behavior of Multi-HBs in Acetic Acid Dimer and Related Species: QTAIM Dual Functional Analysis Employing Perturbed Structures Generated Using Coordinates from Compliance Force Constants

Satoko Hayashi, Taro Nishide, Waro Nakanishi (担当区分： 筆頭著者 )

Bulletin of the Chemical Society of Japan ( The Chemical Society of Japan )  92 ( 1 ) 87 - 96   2019年01月  [査読有り]

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