Article
Chemistry, Organic
Burcu Topaloglu Aksoy, Ahmet Senocak, Ismail Erol, Mehmet F. Saglam, Hakan Kandemir, Ibrahim F. Sengul, Bunyemin Cosut
Summary: In this study, a BODIPY compound (4) bearing a carbazole ring system was successfully synthesized and further used as a building block to construct a new class of bis-BODIPYs (5 and 6) via Suzuki and Stille coupling reactions. The photophysical properties of the targeted BODIPYs were investigated, showing important transitions controlled by solvent polarity. Electrochemical and in situ spectroelectrochemical properties were also studied, revealing the electropolymerizable and electrochromic potentials of the synthesized compounds. These findings suggest the potential applications of compounds 5 and 6 in various electrochemical research areas.
Article
Chemistry, Inorganic & Nuclear
Basvaraj S. Kote, Harish S. Kunchur, Latchupatula Radhakrishna, Madhusudan K. Pandey, Maravanji S. Balakrishna
Summary: The synthesis of a triazole appended dinucleating bisphosphine and its coinage metal complexes were described, including dimeric copper complexes, hetero-cubane silver complex, disilver complexes, dinuclear acetate bridged silver complex, and digold complex. The molecular structures of these complexes were confirmed by single crystal X-ray analysis, showing non-covalent interactions between copper and C-arene.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Yasuhiro Kubota, Masato Nakazawa, Junheon Lee, Ryoma Naoi, Motoki Tachikawa, Toshiyasu Inuzuka, Kazumasa Funabiki, Masaki Matsui, Taekyeong Kim
Summary: The study focused on the synthesis of 1,3- and 1,2-Bis(pyrrol-2-yl)squaraines and discussed their maximum absorption wavelength characteristics. It was found that the thiophene-fused 1,3-squaraine exhibited near-infrared absorption and fluorescence. Additionally, protonation could modulate the absorption wavelength, indicating that mono-cationization is an effective strategy for achieving a red-shift in the wavelength.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Saurabh Kumar, Maravanji S. Balakrishna
Summary: The treatment of large-bite, bisphosphine, 2,6-bis(2-(diphenylphosphanyl)-1H-imidazol-1-yl)-pyridine (BDIP) with various metal complexes resulted in the formation of corresponding chelate complexes with different coordination characteristics. The structures of these complexes were confirmed through single crystal X-ray analysis, revealing variations in ligand bite, M-P bond distances, P···P separation, and dihedral angles.
RESULTS IN CHEMISTRY
(2021)
Article
Chemistry, Organic
V. Vinoth Kumar, P. Gayathri, R. Sankar, C. Arunamaheswari, R. Prasath
Summary: This study examines the influence of molecular planarity and conjugation effects on the physicochemical properties of porphyrin pi-system through a meso-thienyl ring. The synthesized porphyrin compounds, containing thienyl bridged conjugates, show resonance interaction between the porphyrin core and the anthracene/pyrene moiety. These findings contribute to a better understanding of the electron delocalization in these molecules.
POLYCYCLIC AROMATIC COMPOUNDS
(2023)
Article
Chemistry, Physical
Gurjaspreet Singh, Suman, Diksha, Pawan, Mohit, Sushma, Priyanka, Anamika Saini, Pinky Satija
Summary: The synthesized antipyrine-derived triazole-linked bis-organosilane and hybrid silica nanoparticles were characterized and used for colorimetric detection of Fe3+ ions, showing better detection performance. Pharmacokinetic profiles of the alkyne were also examined for effective drug discovery.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Physical
Yun-Shan Xue, Xin-Yue Zhang, Zheng-Chen Tian, Jia-Hao Dai, Yin Wang, Ru-Xiu Tang, Zheng-Hao Fei, Jun Wang
Summary: Two Cd-CPs [Cd(MIP)(BMIOPE)]n (1) and [Cd(NO2-BDC)(BMIOPE)]n (2) were constructed, which can simultaneously detect UO22+, Cr2O72-, CrO42- and NFT with excellent selectivity and sensitivity.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Polymer Science
Kaitie A. Giffin, Virginie Cirriez, Orlando Santoro, Alexandre Welle, Evgueni Kirillov, Jean-Francois Carpentier
Summary: This study reports on the synthesis and separation of a novel metallocene catalyst for olefin polymerization. It demonstrates that the meso isomer of the catalyst outperforms its rac congruent in the polymerization reaction, generating polymer products that are in line with the desired application.
Article
Chemistry, Applied
Fereshteh Azamifar, M. Reza Naimi-Jamal, Oleg M. Demchuk, Agnieszka Szmagara
Summary: Five series of structurally rigid and worthful pentamethine cyanine dyes were successfully synthesized via a simple and efficient approach. The synthesized dyes exhibited excellent photophysical properties, including bright fluorescence, high molar absorption coefficients, and remarkable fluorescence quantum yield. They also demonstrated outstanding stability and resistance to photodecomposition. The presence of pyridinium substituent rings enhanced the rigidity and water solubility of the dyes.
Article
Chemistry, Applied
Anna Pachariyangkun, Praweena Wongkaew, Taweesak Sudyoadsuk, Supawadee Namuangruk, Vinich Promarak
Summary: The development of organic emitters, especially blue ones, is crucial for the advancement of OLEDs in panel display applications. Different conjugated core organic small molecules fluorescent emitters were designed and synthesized for blue OLED application, with C-A-C showing the best device performance, offering low turn-on voltage and high external quantum efficiency.
Article
Chemistry, Multidisciplinary
Andy Shun-Hoi Cheung, Michael Ho-Yeung Chan, Charlotte Po, Eugene Yau-Hin Hong, Vivian Wing-Wah Yam
Summary: The enhanced supramolecular self-assembly behaviors of photo-caged platinum(ii) complexes were triggered by light as the external stimulus, resulting in distinct morphological transformation of the nanoaggregates before and after UV irradiation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Yuto Hino, Shotaro Hayashi
Summary: Acrylonitrile-phenylene-based pi-conjugated molecules have low solubility in various organic solvents due to their highly rigid structures. However, by appending bulky mesityl groups, the solubility of these molecules in different organic solvents can be significantly improved. The solvatochromic behavior and fluorescence properties of these molecules are influenced by their structural flexibility.
Article
Chemistry, Multidisciplinary
Akane Umemiya, Haruyuki Nakano, Nanami Iwaya, Tadaaki Ikoma, Yoshihiro Matano
Summary: Singlet-singlet and triplet-triplet energy-transfer processes between anthracenes and porphyrins were investigated using 3,5-bis(10-phenylanthracen-9-yl)benzene-appended porphyrins (BPABPs). The BPABPs showed efficient intramolecular singlet-singlet energy transfer from the anthracene to the porphyrin unit, as evidenced by significantly quenched fluorescence of the anthracene units. However, intramolecular triplet-triplet energy transfer from the Pt-porphyrin to the anthracene unit was found to be inefficient.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2023)
Article
Chemistry, Multidisciplinary
Andy Shun-Hoi Cheung, Sammual Yu-Lut Leung, Franky Ka-Wah Hau, Vivian Wing-Wah Yam
Summary: The alkynylplatinum(II) bzimpy complexes with trimethylammoniumbenzylethynyl ligand have been synthesized and characterized, showing interesting self-assembly properties in acetonitrile solution. These amphiphilic complexes have been found to form nanorods in electron microscopy experiments, and increasing solvent polarity enhances low-energy emission.
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
(2021)
Article
Biochemistry & Molecular Biology
Simona S. Capomolla, Giacomo Manfroni, Alessandro Prescimone, Edwin C. Constable, Catherine E. Housecroft
Summary: The study reveals the formation of consistent assembly of a (6(5).8) cds net in reactions of cobalt(II) thiocyanate with ligands of different lengths of n-alkyloxy substituents. It is crucial to choose appropriate crystallization solvents for synthesizing crystals, and the n-alkyloxy chains exhibit extended conformations and are accommodated within cavities in the lattice without disrupting the coordination framework.
Article
Chemistry, Multidisciplinary
Takahiro Sakurai, Yuya Hiraoka, Hisaaki Tanaka, Yoshihiro Miyake, Norihito Fukui, Hiroshi Shinokubo
Summary: Ni-II 3,7,13,17-tetrapyridyl-5,15-diazaporphyrin acts as a double tridentate ligand for Pd-II ions, leading to the formation of a pincer-type bispalladium complex. The bispalladium complex exhibits excellent electron accepting ability and reversible redox properties due to the coordination of the two cationic Pd-II centers to the meso-nitrogen atoms. One- and two-electron reduction species of the bispalladium complex have been isolated, characterized, and confirmed to have a 20 pi antiaromatic nature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Masaki Kato, Jinseok Kim, Juwon Oh, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo
Summary: The relationship between the electronic structure and the arrangement of constituent elements in pi-conjugated molecules is discussed. The synthesis and properties of three conjugated hydrocarbons with NIR absorption and emission are described. The effect of pi-extension on achieving a narrow HOMO-LUMO gap with negligible antiaromaticity and diradical character is also discussed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Medicinal
Kazuto Takaishi, Chihiro Maeda, Tadashi Ema
Summary: Circularly polarized luminescence (CPL) dyes, recognized as new generation materials, are actively being developed with the help of molecular recognition systems. CPL can be induced through the mixing of different characteristics of host and guest molecules, providing a more efficient alternative to covalent bonding methods in constructing ordered chiral structures.
Article
Chemistry, Multidisciplinary
Chihiro Maeda, Issa Yasutomo, Kazuto Takaishi, Tadashi Ema
Summary: In this article, recent progress in functional dyes showing circularly polarized luminescence (CPL) containing porphyrins or phthalocyanines is summarized. The CPL-active systems are classified into four categories: (i) porphyrins with chiral sources; (ii) axially chiral porphyrin dimers; (iii) self-assembled porphyrins; (iv) porphyrin-sensitized CPL dyes.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2023)
Article
Chemistry, Multidisciplinary
Shiori Itabuchi, Ryo Nozawa, Takuya Yoshida, Norihito Fukui, Hiroshi Shinokubo
Summary: In this study, a novel norcorrole Ni(II) complex with distinct antiaromatic character was synthesized. The antiaromatic nature of the complex was evaluated using experimental and computational methods, and the differences in molecular structure and crystal packing arrangement were revealed by X-ray diffraction analysis.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2023)
Article
Chemistry, Multidisciplinary
Shiho Mori, Takahiro Sakurai, Tsubasa Nishimura, Norihito Fukui, Yoshihiro Miyake, Hiroshi Shinokubo
Summary: We synthesized a freebase diphenyl diazaporphyrin and its complexes with Ni(II), Cu(II), Pd(II), and Pt(II). These molecules form a one-dimensional pi-stacking array in the solid state. The crystal packing arrangement is dominated by four-fold intermolecular hydrogen bonding interactions between the meso-nitrogen atom of the diazaporphyrin core and the ortho-hydrogen atom of the phenyl substituent. This study demonstrates the potential of using meso-nitrogen atoms in diazaporphyrins as hydrogen bonding acceptors for constructing supramolecular assemblies.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2023)
Article
Chemistry, Organic
Mai Odajima, Norihito Fukui, Hiroshi Shinokubo
Summary: This study reports the synthesis and properties of a dinaphthooxepine bisimide (DNOBI), a nonplanar perylene bisimide (PBI) analogue with an inserted oxygen atom. DNOBI smoothly underwent an oxygen-extrusion reaction upon electron injection at room temperature, yielding PBI in good yield. Studies on the reaction mechanism suggest that the isomerization of DNOBI to dinaphthooxanorcaradiene bisimide upon the injection of two electrons is a key step in inducing the oxygen-extrusion reaction.
Article
Chemistry, Multidisciplinary
Keita Tajima, Kyohei Matsuo, Hiroko Yamada, Norihito Fukui, Hiroshi Shinokubo
Summary: In this study, a strongly electron-accepting pi-system, diazazethrene bisimide (DAZBI), was developed by incorporating imide substituents and imine-type nitrogen atoms into zethrene. DAZBI exhibited a low-lying LUMO (-4.3 eV vs. vacuum) and was readily reduced to the corresponding dihydro species by a weak reductant, l-ascorbic acid. Injection of two electrons into DAZBI resulted in the formation of a stable dianion with intense red fluorescence. Additionally, a DAZBI dimer was synthesized, which effectively accommodated four electrons upon electron injection.
Article
Chemistry, Organic
Chihiro Maeda, Koki Akiyama, Tadashi Ema
Summary: Oxidation of dihydroxyhetero[7]-helicenes resulted in the formation of dihetero[8]-circulenesvia simultaneous C-C coupling and dehydrative furan formation. The synthesized pristine dihetero[8]-circulenes were characterized for the first time, with X-ray crystal structures and DFT-optimized structures revealing distorted saddle-like structures. The degree of distortion was found to be correlated with the photophysical properties.
Article
Chemistry, Multidisciplinary
Yusuke Matsuo, Chihiro Maeda, Yusuke Tsutsui, Takayuki Tanaka, Shu Seki
Summary: The oxidative fusion reaction of cyclic heteroaromatic pentads composed of pyrrole and thiophene can produce closed-heterohelicene monomers and dimers depending on the oxidation conditions. Under specific oxidation conditions, the interconversion between monomers and dimers can be achieved by UV irradiation, accompanied by the observation of circularly polarized luminescence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Sara Suzuki, Soni Aman Govind, Kosuke Imamura, Hideki Yorimitsu, Hiroshi Shinokubo, Masahiro Higashi, Hirofumi Sato
Summary: The radical cyclization reaction in aqueous environment by Yorimitsu et al. was reexamined using the RISM-SCF-cSED method, a hybrid approach combining quantum chemistry and statistical mechanics for molecular liquids. The difference in barrier height between the forward reaction from the intermediate E-rot, the cyclization step, and the backward reaction is crucial for the reaction yield. By considering the effect of hydrogen bonding through the RISM theory, it was found that the barrier height for the forward reaction is lower, particularly in water. In other words, accounting for microscopic solvation effects clearly elucidates the disparity between water and DMSO solvents, explaining the significant acceleration of the reaction in the aqueous environment.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Chemistry, Physical
Zeming Wang, Rui Jing, Yang Li, Di Song, Yan Wan, Norihito Fukui, Hiroshi Shinokubo, Zhuoran Kuang, Andong Xia
Summary: Disulfide bridges in proteins exhibit excellent photostability, while the cleavage and reforming dynamics of disulfide bonds in aromatic compounds are affected by the rigid chemical structure. In this study, the effect of disulfide modification on the excited-state deactivation mechanism was investigated using a model compound with a disulfide five-membered-ring structure. It was found that the excellent photostability was achieved through ultrafast excited-state quenching induced by the S-S stretching, instead of the cleavage of the disulfide bond.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Organic
Chihiro Maeda, Takumi Cho, Ren Kumemoto, Tadashi Ema
Summary: Chemical fixation of CO2 has gained much attention, especially the catalytic formation of C-C bonds with CO2 to produce carboxylic acids. Among various CO2 fixation methods, multiple carboxylation is a challenging subject. In this study, we investigated the Cu-catalyzed carboxylation of various boronic acid pinacol esters (C(sp(2))-, C(sp(3))-, and C(sp)-B compounds) with CO2, which efficiently yielded different carboxylic acids including aryl, alkenyl, alkyl, and alkynyl carboxylic acids. The carboxylation method was also successful in multiple CO2 fixation, leading to the synthesis of di- and tri-carboxylic acids under robust reaction conditions (a total of 29 examples).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Yoshihiro Takeo, Junichiro Hirano, Norihito Fukui, Hiroshi Shinokubo
Summary: We investigated the chemical and physical properties of internally functionalized DBC derivatives. These molecules exhibit chiral double-helicene-like structures that are configurationally stable at ambient temperatures. The conformational change in the excited state is controlled by the internal substituents, thereby modulating the emission intensity. Notably, the DBC derivative with a methylenedioxy unit undergoes aromatization through elimination of the internal substituent upon photoexcitation, resulting in the formation of DBC.
Article
Chemistry, Organic
Yoshihiro Takeo, Junichiro Hirano, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo
Summary: This study compares a bowl-shaped aromatic hydrocarbon with internal methoxy groups to its derivatives with hydrogen, methyl, and anisyl groups. The methoxy-substituted derivative exhibits enhanced electron-accepting properties and changes in absorption properties. The results provide insights into the structure-property relationships in graphene oxide and advanced fullerene receptors.
ORGANIC CHEMISTRY FRONTIERS
(2023)
