Molecular rotors are one of the building blocks of molecular machines and are nano-sized machines with mechanically rotating moieties. Among them, intermeshing triptycenes with a gear-like skeleton allows the construction of a molecular rotor that transmits rotational motion. For triptycenes to mesh with each other without loss of rotation, intermeshing them in parallel and adjusting the distance between their axis to 8.1 Å are required. However, with conventional methods, because of the restrictions on bond lengths and atomic radius, achieving an ideal arrangement in which the triptycenes mesh in parallel at 8.1 Å has been difficult. In this work, we synthesized disulfonic acid containing a triptycene as a rotator, and combining it with amines of two different steric factors (normal-amylamine (nAmA) and guanidine (Gu)) allowed us to prepare organic salts with varying arrangements of triptycene. In the organic salt with the planar amine (Gu), the crystal structure was close to the ideal intermeshing arrangement of triptycene, and the distance between their axis was 7.7 Å. The T1ρ 13C spin-lattice relaxation time by solid-state NMR demonstrated that triptycene rotates efficiently at 24 kHz at 313 K with a low rotational barrier (10.9 kcal/mol) compared to non-intermeshing structures.
分子转子是分子机器的组成部分之一，是具有机械旋转分子的纳米级机器。其中，将具有齿轮状骨架的三庚烯相互啮合，可以构建一个传递旋转运动的分子转子。要使三庚烯相互啮合而不损失旋转，需要将它们平行啮合，并将它们的轴间距调整到 8.1 Å。然而，在传统方法中，由于键长和原子半径的限制，很难实现三庚烯平行啮合在 8.1 Å 的理想排列。在这项工作中，我们合成了含有三庚烯作为旋转剂的二磺酸，并将其与两种不同立体因子的胺（正氨胺（nAmA）和胍胺（Gu））结合，制备出了具有不同三庚烯排列的有机盐。固态核磁共振的 T1ρ 13C 自旋晶格弛豫时间表明，与非啮合结构相比，三庚烯在 313 K 下以 24 kHz 的频率高效旋转，旋转势垒较低（10.9 kcal/mol）。
{"title":"Construction of Triptycene Molecular Rotors with Intermeshing Arrangement and Low Rotational Barrier","authors":"T. Furuta, Kouki Oka, N. Tohnai","doi":"10.1093/bulcsj/uoae013","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae013","url":null,"abstract":"\u0000 Molecular rotors are one of the building blocks of molecular machines and are nano-sized machines with mechanically rotating moieties. Among them, intermeshing triptycenes with a gear-like skeleton allows the construction of a molecular rotor that transmits rotational motion. For triptycenes to mesh with each other without loss of rotation, intermeshing them in parallel and adjusting the distance between their axis to 8.1 Å are required. However, with conventional methods, because of the restrictions on bond lengths and atomic radius, achieving an ideal arrangement in which the triptycenes mesh in parallel at 8.1 Å has been difficult. In this work, we synthesized disulfonic acid containing a triptycene as a rotator, and combining it with amines of two different steric factors (normal-amylamine (nAmA) and guanidine (Gu)) allowed us to prepare organic salts with varying arrangements of triptycene. In the organic salt with the planar amine (Gu), the crystal structure was close to the ideal intermeshing arrangement of triptycene, and the distance between their axis was 7.7 Å. The T1ρ 13C spin-lattice relaxation time by solid-state NMR demonstrated that triptycene rotates efficiently at 24 kHz at 313 K with a low rotational barrier (10.9 kcal/mol) compared to non-intermeshing structures.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139854459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. Agou, Shota Hayama, Naoya Takano, S. Yamada, Tsutomu Konno, Toshiyuki Oshiki, H. Komatsuzaki, Hiroki Fukumoto
Dibenzo-1,4-heteraborins and their π-extended derivatives have been paid increased attention to because of their potential as optical and electronic functional materials such as organic electroluminescence emitters. Meanwhile, 1,4-heteraborin compounds with heteroaromatic ring systems have remained scarce, even though Liu et al. recently reported the synthesis, properties and functionalization of dithieno-1,4-thiaborins (DTTBs). In this work, DTTBs with 10H-phenothiazine-10-yl (Pz), 9H-carbazol-9-yl (Cz), and p-(Ph2N)C6H4 groups as electron-donating amino groups at the α-positions of the thiophene moieties were synthesized using palladium-catalyzed coupling reactions. X-Ray crystallographic analysis revealed the molecular structure of a DTTB substituted with Pz groups. This analysis showed that the two Pz moieties adopted extra- (quasi-axial) conformations. The Cz and p-(Ph2N)C6H4 substituted DTTBs showed red-shifted absorption and emission when compared to the original DTTBs. This shift is due to donor–acceptor interactions between the amino groups and the DTTB cores. The Pz-substituted DTTB exhibited dual fluorescence emissions, originating from the locally-excited (LE) and twisted intramolecular charge transfer (TICT) states. The intensity and nature of these emissions varied based on solvent polarity, temperature, and viscosity, suggesting the potential of the Pz-substituted DTTB to act as a fluorescent environment sensor.
{"title":"Synthesis and Optical Properties of Dithieno-1,4-Thiaborins Bearing Electron-Donating Amino Groups","authors":"T. Agou, Shota Hayama, Naoya Takano, S. Yamada, Tsutomu Konno, Toshiyuki Oshiki, H. Komatsuzaki, Hiroki Fukumoto","doi":"10.1093/bulcsj/uoae014","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae014","url":null,"abstract":"\u0000 Dibenzo-1,4-heteraborins and their π-extended derivatives have been paid increased attention to because of their potential as optical and electronic functional materials such as organic electroluminescence emitters. Meanwhile, 1,4-heteraborin compounds with heteroaromatic ring systems have remained scarce, even though Liu et al. recently reported the synthesis, properties and functionalization of dithieno-1,4-thiaborins (DTTBs). In this work, DTTBs with 10H-phenothiazine-10-yl (Pz), 9H-carbazol-9-yl (Cz), and p-(Ph2N)C6H4 groups as electron-donating amino groups at the α-positions of the thiophene moieties were synthesized using palladium-catalyzed coupling reactions. X-Ray crystallographic analysis revealed the molecular structure of a DTTB substituted with Pz groups. This analysis showed that the two Pz moieties adopted extra- (quasi-axial) conformations. The Cz and p-(Ph2N)C6H4 substituted DTTBs showed red-shifted absorption and emission when compared to the original DTTBs. This shift is due to donor–acceptor interactions between the amino groups and the DTTB cores. The Pz-substituted DTTB exhibited dual fluorescence emissions, originating from the locally-excited (LE) and twisted intramolecular charge transfer (TICT) states. The intensity and nature of these emissions varied based on solvent polarity, temperature, and viscosity, suggesting the potential of the Pz-substituted DTTB to act as a fluorescent environment sensor.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139797203","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. Agou, Shota Hayama, Naoya Takano, S. Yamada, Tsutomu Konno, Toshiyuki Oshiki, H. Komatsuzaki, Hiroki Fukumoto
Dibenzo-1,4-heteraborins and their π-extended derivatives have been paid increased attention to because of their potential as optical and electronic functional materials such as organic electroluminescence emitters. Meanwhile, 1,4-heteraborin compounds with heteroaromatic ring systems have remained scarce, even though Liu et al. recently reported the synthesis, properties and functionalization of dithieno-1,4-thiaborins (DTTBs). In this work, DTTBs with 10H-phenothiazine-10-yl (Pz), 9H-carbazol-9-yl (Cz), and p-(Ph2N)C6H4 groups as electron-donating amino groups at the α-positions of the thiophene moieties were synthesized using palladium-catalyzed coupling reactions. X-Ray crystallographic analysis revealed the molecular structure of a DTTB substituted with Pz groups. This analysis showed that the two Pz moieties adopted extra- (quasi-axial) conformations. The Cz and p-(Ph2N)C6H4 substituted DTTBs showed red-shifted absorption and emission when compared to the original DTTBs. This shift is due to donor–acceptor interactions between the amino groups and the DTTB cores. The Pz-substituted DTTB exhibited dual fluorescence emissions, originating from the locally-excited (LE) and twisted intramolecular charge transfer (TICT) states. The intensity and nature of these emissions varied based on solvent polarity, temperature, and viscosity, suggesting the potential of the Pz-substituted DTTB to act as a fluorescent environment sensor.
{"title":"Synthesis and Optical Properties of Dithieno-1,4-Thiaborins Bearing Electron-Donating Amino Groups","authors":"T. Agou, Shota Hayama, Naoya Takano, S. Yamada, Tsutomu Konno, Toshiyuki Oshiki, H. Komatsuzaki, Hiroki Fukumoto","doi":"10.1093/bulcsj/uoae014","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae014","url":null,"abstract":"\u0000 Dibenzo-1,4-heteraborins and their π-extended derivatives have been paid increased attention to because of their potential as optical and electronic functional materials such as organic electroluminescence emitters. Meanwhile, 1,4-heteraborin compounds with heteroaromatic ring systems have remained scarce, even though Liu et al. recently reported the synthesis, properties and functionalization of dithieno-1,4-thiaborins (DTTBs). In this work, DTTBs with 10H-phenothiazine-10-yl (Pz), 9H-carbazol-9-yl (Cz), and p-(Ph2N)C6H4 groups as electron-donating amino groups at the α-positions of the thiophene moieties were synthesized using palladium-catalyzed coupling reactions. X-Ray crystallographic analysis revealed the molecular structure of a DTTB substituted with Pz groups. This analysis showed that the two Pz moieties adopted extra- (quasi-axial) conformations. The Cz and p-(Ph2N)C6H4 substituted DTTBs showed red-shifted absorption and emission when compared to the original DTTBs. This shift is due to donor–acceptor interactions between the amino groups and the DTTB cores. The Pz-substituted DTTB exhibited dual fluorescence emissions, originating from the locally-excited (LE) and twisted intramolecular charge transfer (TICT) states. The intensity and nature of these emissions varied based on solvent polarity, temperature, and viscosity, suggesting the potential of the Pz-substituted DTTB to act as a fluorescent environment sensor.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139857447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Host materials with external heavy atom effects do not change the chemical structures of incorporated luminescent molecules but promote intersystem crossing from the excited singlet state to the excited triplet state, which induces room-temperature phosphorescence (RTP). The deuteration of luminescent molecules suppresses non-radiative deactivation via C–H stretching vibration; therefore, the improvement of both phosphorescence lifetime and quantum efficiency (i.e. isotope effect) is expected. Although a combination of the external heavy atom effect and isotope effect could be expected to improve phosphorescent performances dramatically, an environment with a strong external heavy atom effect (density of iodine atoms ≥0.65 gcm−3) increases non-radiative deactivation via spin-orbit coupling; therefore, the isotope effect is hindered, and the phosphorescent lifetime and quantum efficiency are not usually improved. In the current work, we constructed cage-like sodalite-type porous organic salts (s-POSs) where the density of iodine atoms (0.55 gcm−3) was moderate (0.13 ̶ 0.65 gcm−3). Incorporation of a deuterated representative luminescent molecule such as coronene (coronene-d12) into s-POSs enabled the exerting of both the external heavy atom effect and isotope effect, which successfully improved both RTP lifetime (1.1 times) and quantum efficiency (1.6 times) over those of an incorporated ordinary coronene (coronene-h12).
{"title":"Incorporation of deuterated coronene into cage-like sodalite-type porous organic salts and improvement of room-temperature phosphorescence properties","authors":"Hiroi Sei, Kouki Oka, T. Furuta, N. Tohnai","doi":"10.1093/bulcsj/uoad023","DOIUrl":"https://doi.org/10.1093/bulcsj/uoad023","url":null,"abstract":"\u0000 Host materials with external heavy atom effects do not change the chemical structures of incorporated luminescent molecules but promote intersystem crossing from the excited singlet state to the excited triplet state, which induces room-temperature phosphorescence (RTP). The deuteration of luminescent molecules suppresses non-radiative deactivation via C–H stretching vibration; therefore, the improvement of both phosphorescence lifetime and quantum efficiency (i.e. isotope effect) is expected. Although a combination of the external heavy atom effect and isotope effect could be expected to improve phosphorescent performances dramatically, an environment with a strong external heavy atom effect (density of iodine atoms ≥0.65 gcm−3) increases non-radiative deactivation via spin-orbit coupling; therefore, the isotope effect is hindered, and the phosphorescent lifetime and quantum efficiency are not usually improved. In the current work, we constructed cage-like sodalite-type porous organic salts (s-POSs) where the density of iodine atoms (0.55 gcm−3) was moderate (0.13 ̶ 0.65 gcm−3). Incorporation of a deuterated representative luminescent molecule such as coronene (coronene-d12) into s-POSs enabled the exerting of both the external heavy atom effect and isotope effect, which successfully improved both RTP lifetime (1.1 times) and quantum efficiency (1.6 times) over those of an incorporated ordinary coronene (coronene-h12).","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140466949","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Junhui Zhao, Tao Wu, Qishan He, Huiyuan Fang, Mingshuang Liu, Yumin Liu, Zijian Zhou, Junyu Zhang, Weihua Yang
The zeolitic imidazolate framework-8 (ZIF-8)-derived Fe-N/C catalysts show excellent oxygen reduction reactions (ORR) performance, but the harsh synthesis conditions and low yields have greatly limited their commercialization. Herein, we report an electrochemical-assisted polymerization method to produce a Fe-N/C structure (EC-Fe-N/C) with a high surface area (954.583 m2 g−1), high dispersion of Fe (2.2 wt %), and abundant N (2.05 wt %). The hierarchical structure exhibits excellent ORR activity (half-wave potential 0.88 V, in alkaline media) and outstanding zinc-air battery performance (energy density 821.3 mAh g−1 Zn, specific capacity 1017.1 Wh kg−1 Zn). This work may provide a simple and effective strategy to rationally design the Fe-N/C porous structure for highly efficient ORR activity.
{"title":"Electrochemically assisted polymerization synthesis of ZIF-derived Fe-N/C with high oxygen reduction reaction activity","authors":"Junhui Zhao, Tao Wu, Qishan He, Huiyuan Fang, Mingshuang Liu, Yumin Liu, Zijian Zhou, Junyu Zhang, Weihua Yang","doi":"10.1093/bulcsj/uoae015","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae015","url":null,"abstract":"\u0000 The zeolitic imidazolate framework-8 (ZIF-8)-derived Fe-N/C catalysts show excellent oxygen reduction reactions (ORR) performance, but the harsh synthesis conditions and low yields have greatly limited their commercialization. Herein, we report an electrochemical-assisted polymerization method to produce a Fe-N/C structure (EC-Fe-N/C) with a high surface area (954.583 m2 g−1), high dispersion of Fe (2.2 wt %), and abundant N (2.05 wt %). The hierarchical structure exhibits excellent ORR activity (half-wave potential 0.88 V, in alkaline media) and outstanding zinc-air battery performance (energy density 821.3 mAh g−1 Zn, specific capacity 1017.1 Wh kg−1 Zn). This work may provide a simple and effective strategy to rationally design the Fe-N/C porous structure for highly efficient ORR activity.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140470116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The reaction of 2-nitro-3,3′-bi(1-benzothiophene) bearing ester groups at 7- and 7′-positions under the Cadogan cyclization conditions (PPh3, o-C6H4Cl2, refl.) afforded the targeted 10H-di(1-benzothiopheno)[2,3-b:3′,2′-d]pyrrole-1,8- dicarboxylate derivative in a low yield accompanied with a byproduct. On the other hand, the Cadogan reaction of 2-nitro-3,3′-bi(1-benzothiophene) without ester groups did not provide the corresponding pyrrole at all but gave a mixture of thiophene-ring-opening products, from which dibenzothio- phenothiopyrans were isolated. The structures of these ring-opening products were fully characterized by spectroscopic and X-ray analyses and the generation mechanism giving the byproducts was deduced. Pristine 10H-di(1-benzothiopheno)[2,3-b:3′,2′-d]pyrrole could be prepared via another route, namely nitrosation followed by cyclization and reduction.
{"title":"Synthesis of 10H-di(1-benzothiopheno)[2,3-b:3′,2′-d]pyrrole: Re-investigation of the Cadogan cyclization route","authors":"Yuma Tanioka, Shigeki Mori, M. Takase, H. Uno","doi":"10.1093/bulcsj/uoae010","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae010","url":null,"abstract":"\u0000 The reaction of 2-nitro-3,3′-bi(1-benzothiophene) bearing ester groups at 7- and 7′-positions under the Cadogan cyclization conditions (PPh3, o-C6H4Cl2, refl.) afforded the targeted 10H-di(1-benzothiopheno)[2,3-b:3′,2′-d]pyrrole-1,8- dicarboxylate derivative in a low yield accompanied with a byproduct. On the other hand, the Cadogan reaction of 2-nitro-3,3′-bi(1-benzothiophene) without ester groups did not provide the corresponding pyrrole at all but gave a mixture of thiophene-ring-opening products, from which dibenzothio- phenothiopyrans were isolated. The structures of these ring-opening products were fully characterized by spectroscopic and X-ray analyses and the generation mechanism giving the byproducts was deduced. Pristine 10H-di(1-benzothiopheno)[2,3-b:3′,2′-d]pyrrole could be prepared via another route, namely nitrosation followed by cyclization and reduction.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140480241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Mn(III)-based oxidation of tetracarbonyl compounds with 1,1-diarylethenes formed dioxapropellanes. The use of methylenebis(3-hydroxycyclohex-2-en-1-one)s as a tetracarbonyl compound led to the production of 3,4,5,6,7,9-hexahydro-8H-4a,9a-(epoxyethano)xanthene-1,8(2H)-diones in good yields. Although the reaction competed with the self-cyclization to form 3,5,6,7-tetrahydro-4H-spiro[benzofuran-2,1'-cyclohexane]-2’,4,6'-triones, it could be controlled by adding the co-solvent formic acid at room temperature. The reactions of alkyl- and aryl-substituted methylenebis(3-hydroxycyclohex-2-en-1-one)s resulted in the corresponding dioxapropellanes as a diastereomixture. The formation of the diastereomers was explained by the steric hindrance of the intermediate carbocations during the tandem cyclization. The reactions using 2-(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-en-1-yl)butane-1,4-diones and 2,2'-methylenebis(3-hydroxycyclopent-2-en-1-one)s also produced the corresponding dioxapropellanes. The structure determination of the products and the reaction pathway for the formation of the dioxapropellanes are discussed.
{"title":"Synthesis of Dioxapropellanes Using Mn(III)-Based Oxidative Tandem Cyclization of Tetracarbonyl Compounds with Diarylethenes","authors":"Keisuke Shibuya, Ayaka Chikamatsu, Kazuki Hisano, Hiroshi Nishino","doi":"10.1093/bulcsj/uoae011","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae011","url":null,"abstract":"\u0000 The Mn(III)-based oxidation of tetracarbonyl compounds with 1,1-diarylethenes formed dioxapropellanes. The use of methylenebis(3-hydroxycyclohex-2-en-1-one)s as a tetracarbonyl compound led to the production of 3,4,5,6,7,9-hexahydro-8H-4a,9a-(epoxyethano)xanthene-1,8(2H)-diones in good yields. Although the reaction competed with the self-cyclization to form 3,5,6,7-tetrahydro-4H-spiro[benzofuran-2,1'-cyclohexane]-2’,4,6'-triones, it could be controlled by adding the co-solvent formic acid at room temperature. The reactions of alkyl- and aryl-substituted methylenebis(3-hydroxycyclohex-2-en-1-one)s resulted in the corresponding dioxapropellanes as a diastereomixture. The formation of the diastereomers was explained by the steric hindrance of the intermediate carbocations during the tandem cyclization. The reactions using 2-(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-en-1-yl)butane-1,4-diones and 2,2'-methylenebis(3-hydroxycyclopent-2-en-1-one)s also produced the corresponding dioxapropellanes. The structure determination of the products and the reaction pathway for the formation of the dioxapropellanes are discussed.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140490067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This review introduces the preparation, observation, and characterization of systems of molecule polaritons. We summarize recent progress by our group on the control of molecular properties in the spaces of various optical cavities, such as plasmonic metal nanostructures and Fabry-Perot mirrors. After stating our motivations, we introduce topics on single-molecule observations based on surface-enhanced Raman scattering (SERS) spectroscopy. Our original findings are not limited to the ultra-sensitive detection of molecules/materials, but include unique resonant enhancements of SERS through exotic electronic excitation processes at electrified interfaces. Comprehensive analyses of SERS spectra provide novel routes to electronic excitation using plasmonic metal nanostructures. This behavior leads to the distinct photo-energy conversion based on excited electrons and holes with anomalous electrochemical potentials. Such unique resonant electronic excitation emerges a large optical force that can be used to manipulate small single molecules on surfaces in solution, even at room temperature. We also introduce systems for examining unique interactions between molecules and the optical modes of cavities, from single molecules to molecular ensembles. Plasmonic surface lattices and Fabry–Perot mirrors allow the formation of electronic and vibrational strong coupling states, respectively, showing unique properties of molecule polaritons, even under dark conditions, i.e., without photo-illumination.
{"title":"Beyond Single-Molecule Chemistry for Electrified Interfaces using Molecule Polaritons","authors":"Nobuaki Oyamada, Hiro Minamimoto, Tomohiro Fukushima, Ruifeng Zhou, Kei Murakoshi","doi":"10.1093/bulcsj/uoae007","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae007","url":null,"abstract":"\u0000 This review introduces the preparation, observation, and characterization of systems of molecule polaritons. We summarize recent progress by our group on the control of molecular properties in the spaces of various optical cavities, such as plasmonic metal nanostructures and Fabry-Perot mirrors. After stating our motivations, we introduce topics on single-molecule observations based on surface-enhanced Raman scattering (SERS) spectroscopy. Our original findings are not limited to the ultra-sensitive detection of molecules/materials, but include unique resonant enhancements of SERS through exotic electronic excitation processes at electrified interfaces. Comprehensive analyses of SERS spectra provide novel routes to electronic excitation using plasmonic metal nanostructures. This behavior leads to the distinct photo-energy conversion based on excited electrons and holes with anomalous electrochemical potentials. Such unique resonant electronic excitation emerges a large optical force that can be used to manipulate small single molecules on surfaces in solution, even at room temperature. We also introduce systems for examining unique interactions between molecules and the optical modes of cavities, from single molecules to molecular ensembles. Plasmonic surface lattices and Fabry–Perot mirrors allow the formation of electronic and vibrational strong coupling states, respectively, showing unique properties of molecule polaritons, even under dark conditions, i.e., without photo-illumination.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140486874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wataru Yoshida, Yasuteru Shigeta, Hiroshi Matsui, Hajime Miyamoto, R. Kishi, Yasutaka Kitagawa
We theoretically investigated molecular charge populations of one-dimensional (1D) π-stacked multimers consisting of π-conjugated molecules in the neutral and electron oxidation states based on the valence-bond (VB) theory. Qualitative analysis for a π-stacked trimer model based on the VB mixing diagram suggested that the inner monomer site tends to be more positively charged than the outer sites in the monocationic π-stacked trimer. Spatial expansion of each molecular site orbital toward the stacking direction is predicted to enhance the difference of positive charge populations between the inner and outer monomers. In contrast, an opposite tendency for the site charges was expected in the dicationic π-stacked trimer, primarily due to the hole-hole Coulomb repulsions. To generalize the results of the trimer to π-stacked N-mers, 1D N-site VB configuration interaction (VBCI) models were constructed considering the orbital expansion effects between the sites. We examined how the number of monomers (N), stacking distance (R), and characteristic orbital exponent for the monomers (ζ) affect the molecular charge populations in the monocationic and dicationic π-stacked N-mers through the parameters χij characterizing the orbital expansion effect. The results are expected to help establish design strategies for novel electronic functional materials based on discrete stacks of π-conjugated molecules.
我们基于价键（VB）理论，从理论上研究了由中性态和电子氧化态的π共轭分子组成的一维（1D）π堆积多聚体的分子电荷群。根据 VB 混合图对π堆叠三聚体模型进行的定性分析表明，在单配位π堆叠三聚体中，内部单体位点往往比外部位点带更多正电荷。根据预测，每个分子位点轨道向堆叠方向的空间扩展会增强内外单体之间的正电荷群差异。相反，在双阳离子π堆叠三聚体中，预计位点电荷会出现相反的趋势，这主要是由于空穴-空穴库仑斥力造成的。为了将三聚体的结果推广到π堆叠 N 聚体，我们构建了一维 N 位点 VB 构型相互作用（VBCI）模型，其中考虑到了位点之间的轨道扩展效应。我们研究了单体数量（N）、堆积距离（R）和单体的特征轨道指数（ζ）如何通过表征轨道扩展效应的参数 χij 影响单位和双位π堆积 N-聚合物中的分子电荷群。这些结果有望帮助建立基于离散的π-共轭分子堆栈的新型电子功能材料的设计策略。
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Y. Kameda, Misaki Kowaguchi, Y. Amo, T. Usuki, Kazuhiro Nawa, Taku J Sato
Microscopic structure of 10 mol% NaFSA (FSA: bis(fluorosulfonyl)amide) -propylene carbonate (PC) solution has been investigated by means of X-ray and neutron diffraction techniques. Solvation structure of Na+ has been determined from the least squares fitting analysis of X-ray intermolecular difference interference terms observed for 10 mol% NaFSA-PC solution and pure liquid PC. In the present solution, on the average, 6(1) PC molecules are involved in the first solvation shell of Na+ with intermolecular distance, rNaO = 2.26(7) Å and bond angle, ∠Na+…O = C = 169(9)°. Intermolecular correlation between neighboring PC molecules in the solution has been derived from the simultaneous least squares fitting analysis of observed H-H, H-X and X-X (X: atoms except for H) intermolecular partial structure factors determined from neutron diffraction data for H/D isotopically substituted sample solutions. An indication of anti-parallel configuration of the nearest neighbor PC molecules has been suggested.
通过 X 射线和中子衍射技术研究了 10 mol% NaFSA（FSA：双（氟磺酰）酰胺）-碳酸丙烯酯（PC）溶液的微观结构。通过对 10 摩尔 NaFSA-PC 溶液和纯液态 PC 分子间差分干扰项的最小二乘拟合分析，确定了 Na+ 的溶解结构。在本溶液中，平均有 6(1) 个 PC 分子参与 Na+ 的第一溶壳，分子间距为 rNaO = 2.26(7) Å，键角为 ∠Na+...O = C = 169(9)°。溶液中相邻 PC 分子之间的分子间相关性是通过同时对 H/D 同位素置换样品溶液的中子衍射数据中观察到的 H-H、H-X 和 X-X（X：除 H 原子外的其他原子）分子间部分结构因子进行最小二乘法拟合分析得出的。结果表明，最近相邻的 PC 分子具有反平行构型。
{"title":"Local Structure of Concentrated NaFSA Solutions in Propylene Carbonate Studied by X-ray and Neutron Diffraction Methods","authors":"Y. Kameda, Misaki Kowaguchi, Y. Amo, T. Usuki, Kazuhiro Nawa, Taku J Sato","doi":"10.1093/bulcsj/uoae006","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae006","url":null,"abstract":"\u0000 Microscopic structure of 10 mol% NaFSA (FSA: bis(fluorosulfonyl)amide) -propylene carbonate (PC) solution has been investigated by means of X-ray and neutron diffraction techniques. Solvation structure of Na+ has been determined from the least squares fitting analysis of X-ray intermolecular difference interference terms observed for 10 mol% NaFSA-PC solution and pure liquid PC. In the present solution, on the average, 6(1) PC molecules are involved in the first solvation shell of Na+ with intermolecular distance, rNaO = 2.26(7) Å and bond angle, ∠Na+…O = C = 169(9)°. Intermolecular correlation between neighboring PC molecules in the solution has been derived from the simultaneous least squares fitting analysis of observed H-H, H-X and X-X (X: atoms except for H) intermolecular partial structure factors determined from neutron diffraction data for H/D isotopically substituted sample solutions. An indication of anti-parallel configuration of the nearest neighbor PC molecules has been suggested.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139601987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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