Article
Chemistry, Organic
Xinyue Tian, Yao Xiao, Shuoyingjie Wang, Guanghua Liu, Wenhao Zhang, Laiyun Zhou, Jianye Gong, Xuejin Zhang, Xiang Li, He Meng, Jianguo Wang, Gaole Dai, Qing Wang
Summary: Incorporating two pyrrole subunits at the bay positions of perylene-diimide, PDI-2N, with a bowl depth of 1.52 angstrom, was successfully synthesized via one step Buchwald-Hartwig reaction. Despite the electron-rich pyrrole embedding, the radical anion and dianion of PDI-2N were easily prepared and investigated experimentally and theoretically. Furthermore, PDI-2N crystallized in different manners under distinct conditions, forming tubular crystals with infinite two-directional columnar stacking under DMF conditions. This discovery presents a promising bowl-shaped PDI derivative for organoelectronics.
Article
Chemistry, Organic
Yuki Tanaka, Kyohei Matsuo, Hiroko Yamada, Norihito Fukui, Hiroshi Shinokubo
Summary: Preparation of organic semiconductors by solution processes is desirable for flexible electronic devices. Our group reported new soluble precursors that can be transformed into n-type organic semiconductors through heating or light-irradiation. We developed a second-generation synthetic route to enable large-scale and diverse preparation of various N-substituted DNTBIs and identified suitable combinations of leaving group, external stimulus, and N-substituent for efficient charge transport.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Fang Zhang, Zhiwei Zhang, Long Deng, Huichao Guo, Tong Xia, Wenxuan Mao, Junji Zhang
Summary: In this study, novel methylthiophene/benzo[b]thiophene perylene bisimide thiol-precursors were introduced, which would generate thiols via a green-light-induced photorearrangement. The photoreleased thiols enabled a subsequent thiol-ene click ligation with electron deficient substrates without the need for washing. Additionally, the intrinsic fluorescence evolution from the rearrangement of perylene bisimide scaffolds allowed for self-reporting of the entire thiol formation process, enhancing the versatility of applications.
Article
Chemistry, Applied
Ying Wang, Qi Zhang, Junbo Gong, Xin Zhang
Summary: By twisting the aromatic -system structures, highly fluorescent dyes with fluorescence quantum yields close to 100% can be synthesized. These twisted dyes are more sensitive to microenvironment changes, suitable for optoelectrical devices and materials, and retain excellent optical properties.
Article
Chemistry, Multidisciplinary
Zhibin Feng, Jiadong Zhou, Xiandong He, Bohan Wang, Guojing Xie, Xianfeng Qiao, Linlin Liu, Zengqi Xie, Yuguang Ma
Summary: Researchers have successfully developed two diradicals with super stability by increasing conjugation and electron-withdrawing effects, which expands the potential applications of organic spintronic devices.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Oliver Nagler, Kazutaka Shoyama, Olga Anhalt, Matthias Stolte, Rajeev K. Dubey, Zengqi Xie, Frank Wuerthner
Summary: In this study, a new synthetic strategy was reported to control the structural and fluorescence properties of perylene bisimide (PBI) dyes by employing a 1,12-bay-substitution pattern. Novel perylene dyes with excellent structural and optical properties were successfully obtained through further functionalization of 1,12-dihydroxy-PBI derivatives.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Engineering, Electrical & Electronic
Vinod Kumar Vishwakarma, Mrinmoy Roy, Rajan Singh, Doddamane Sreenivasamurthy Shankar Rao, Roy Paily, Achalkumar Ammathnadu Sudhakar
Summary: Researchers designed and synthesized four imidazole-containing liquid-crystalline compounds based on naphthalene and perylene bisimide. These compounds possessed liquid crystallinity and solution processability, making them suitable for use as organic semiconductors. The compounds exhibited different columnar phases, with greater thermal stability and lower band gaps observed in both naphthalene and perylene bisimide derivatives. Two of the compounds were used for the fabrication of organic field-effect transistors, demonstrating high hole mobility in normal air conditions.
ACS APPLIED ELECTRONIC MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Manuel A. Martinez, Elisa E. Greciano, Jorge Cuellar, Jose M. Valpuesta, Luis Sanchez
Summary: In this study, a highly emissive amphiphilic N-annulated PBI 1 decorated with oligo ethylene glycol (OEG) side chains was synthesized. Compound 1 self-assembles in water to form globular aggregates, demonstrating good solubility and stability in aqueous media. The UV-Vis spectra and solvent denaturation experiments provided insights into the self-assembly process and stability of compound 1 in different solvents.
Article
Engineering, Electrical & Electronic
Vinod Kumar Vishwakarma, Mrinmoy Roy, Rajan Singh, Doddamane Sreenivasamurthy Shankar Rao, Roy Paily, Achalkumar Ammathnadu Sudhakar
Summary: We designed and synthesized four liquid-crystalline derivatives based on naphthalene and perylene bisimide with imidazole-containing groups. These compounds with 10 flexible peripheral chains possess liquid crystallinity and solution processability, suitable for use as organic semiconductors. They showed different columnar phases and exhibited higher thermal stability and lower band gaps. The NI derivatives showed larger Stokes shifts, while the PI derivatives exhibited very high molar extinction coefficients. Two solution-processable liquid-crystalline compounds (NI-12 and PI-12) were used to fabricate organic field-effect transistors, with NI-12 derivatives showing a hole mobility of 1.99 cm2/V center dot s and PI-12 derivatives showing a hole mobility of 0.63 cm2/V center dot s at room temperature in normal air conditions.
ACS APPLIED ELECTRONIC MATERIALS
(2023)
Article
Chemistry, Organic
Guangwei Shao, Mingliang Wu, Xin Wang, Jingjing Zhao, Xiaoxiao You, Di Wu, Jianlong Xia
Summary: Here, we present a simple synthesis method for the preparation of 1,6-disubstituted perylene diimide using a tetrabromo-perylene monoimide as the starting material. Through a selective methoxylation, domino carbonylative amidation, demethylation, and triflation sequence, the desired product can be obtained in satisfactory yield. Moreover, the obtained compound can be further used in Suzuki and Sonogashira cross coupling reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Manuel A. Martinez, Daniel Aranda, Enrique Orti, Juan Arago, Luis Sanchez
Summary: The self-assembling features of amphiphilic N-annulated perylene bisimides (N-PBIs) 1-4 in water were investigated experimentally and theoretically. The hydrophilic/hydrophobic ratio, determined by the oligo(ethylene) glycol (OEG) chains in the monomers, plays a significant role in the enthalpy of self-assembly. Molecular dynamic simulations revealed the influence of the initial arrangement of hydrophilic side chains and water-side chain interactions on the enthalpy contribution and overall stability of the aggregated species in water.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Iris Solymosi, Christian Neiss, Harald Maid, Frank Hampel, Thomas Solymosi, Andreas Gorling, Andreas Hirsch, M. Eugenia Perez-Ojeda
Summary: Crystal packing and chromophore communication play vital roles in applications related to light-energy harvesting and conversion. Obtaining crystals with flexible and soluble structures is challenging. However, a crystal structure of a highly flexible perylene-3,4 : 9,10-tetracarboxylic acid bisimide (PBI) cyclophane has been successfully obtained and analyzed, revealing a unique one-dimensional pi-stacking supramolecular polymer-like structure. The findings highlight the importance of crystal packing control for specific applications based on multiexciton generation processes.
Article
Chemistry, Multidisciplinary
Kevin Bold, Matthias Stolte, Kazutaka Shoyama, Ana-Maria Krause, Alexander Schmiedel, Marco Holzapfel, Christoph Lambert, Frank Wuerthner
Summary: In this study, a series of donor-acceptor macrocyclic dyads were synthesized and characterized. It was found that controlling the conformation of the macrocycle allowed for fine tuning of the absorption spectra, and the size of the oligothiophene bridge played a role in the fast charge transfer process in the excited state dynamics.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Sachin D. Padghan, Min-Chieh Chung, Qi-Sheng Zhang, Wei-Chun Lin, Kew-Yu Chen
Summary: In this study, a series of perylene bisimide compounds with different substituents were synthesized. The substituents were found to affect the absorption and fluorescence wavelengths of the compounds. One compound also exhibited colorimetric and turn-on fluorescence responses under extremely acidic conditions.
Article
Chemistry, Multidisciplinary
Kevin Bold, Matthias Stolte, Kazutaka Shoyama, Marco Holzapfel, Alexander Schmiedel, Christoph Lambert, Frank Wuerthner
Summary: Two macrocyclic architectures comprising oligothiophene strands that connect the imide positions of a perylene biscimide (PBI) dye have been synthesized via a platinum-mediated cross-coupling strategy. The crystal structure of the double bridged PBI reveals all syn-arranged thiophene units enclosed a planar PBI chromophore via a 12-membered macrocycle. The target structures exhibit ultrafast Forster Resonance Energy Transfer and photoinduced electron transfer, resulting in extremely low fluorescence quantum yields even in the lowest polarity cyclohexane solvent.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Kenta Tamaki, Sougata Datta, Keigo Tashiro, Atsushi Isobe, Fabien Silly, Shiki Yagai
Summary: The supramolecular polymerization of two regioisomeric naphthalene-azobenzene dyads bearing barbituric acid and tri(dodecyloxy)phenyl units in nonpolar solvent was studied, revealing considerable differences in their topologies. One isomer formed randomly coiled supramolecular polymers with intrinsic curvature, while the other formed linearly extended supramolecular polymers. Only the former showed a large topological change upon photo-irradiation due to different geometrical changes accompanied with photoisomerization of the azobenzene unit. These differences were attributed to the distinct geometries of supermacrocyclic hydrogen-bonded intermediates (rosettes).
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Kenta Kato, Tomohiro Seki, Hajime Ito
Summary: The first examples of single crystals exhibiting salient effects by different structure change mechanisms are reported, including photodimerization reaction-induced photosalient effect and anisotropic thermal contraction-induced thermosalient effect. Multiple jumps of crystals by cooling and then UV irradiation are demonstrated for the programmed motion of molecular crystals.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Takuya Fukushima, Kenta Tamaki, Atsushi Isobe, Takashi Hirose, Nobutaka Shimizu, Hideaki Takagi, Rie Haruki, Shin-ichi Adachi, Martin J. Hollamby, Shiki Yagai
Summary: The research investigates the helical folding mechanism of a novel type of SPs, realizing a reversible folding/unfolding process driven by photoisomerization. The helical folding is driven by internal structure ordering of the SP fiber that repairs defects and occurs only for the resulting helicoidal structure.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Keigo Tashiro, Kosuke Katayama, Kenta Tamaki, Luca Pesce, Nobutaka Shimizu, Hideaki Takagi, Rie Haruki, Martin J. Hollamby, Giovanni M. Pavan, Shiki Yagai
Summary: The research explores the feasibility of using external stimuli to induce non-uniform structural transformation of supramolecular polymer chains for the preparation of one-dimensional nanofibers with distinct topological domains. UV-light induced nonuniform unfolding of the newly prepared helically folded supramolecular polymers, resulting in topological block copolymers consisting of folded and unfolded domains.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jorge S. Valera, Hironari Arima, Cristina Naranjo, Takuho Saito, Natsuki Suda, Rafael Gomez, Shiki Yagai, Luis Sanchez
Summary: The hierarchical self-assembly of scissor-shaped azobenzene dyads leads to the formation of discrete nanotoroids in solution, which further organize into well-defined 2D porous networks on a graphite surface. The steric demand of peripheral aliphatic units controls the stackability of nanotoroids in solution. Additionally, reversible dissociation and reconstruction of nanotoroids can be achieved through UV and visible light photoirradiation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Keigo Tashiro, Takuho Saito, Hironari Arima, Natsuki Suda, Balaraman Vedhanarayanan, Shiki Yagai
Summary: Chemists have constructed sophisticated artificial nanostructured systems through self-assembly, including scissor-shaped photochromic dyads that hierarchically self-assemble into discrete nanostructures with photoresponsive properties. These nanostructures, such as azobenzene dyads, can be dissociated and reorganized through the photoisomerization of azobenzene units, enabling controllable and adjustable structures.
Article
Chemistry, Physical
Fabien Silly, Maika Kawaura, Takumi Aizawa, Hayato Ouchi, Shiki Yagai
Summary: The self-assembled structures of a hydrogen-bonding oligo(thiophene) molecule functionalized with a barbiturate unit were investigated at different hierarchical levels. It was found that two distinct molecular self-assembly pathways exist, leading to the formation of rodlike and helical nanofibers.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Maika Kawaura, Takumi Aizawa, Sho Takahashi, Hiroshi Miyasaka, Hikaru Sotome, Shiki Yagai
Summary: The study demonstrates that barbiturate-based molecules can form nanostructures through supramolecular polymerization under specific conditions, enhancing the emission efficiency. Additionally, the positional difference in regioisomers also influences the interchain association of supramolecular polymers, resulting in different luminescent soft materials.
Article
Chemistry, Multidisciplinary
Natsuki Suda, Takuho Saito, Hironari Arima, Shiki Yagai
Summary: Recent advances in supramolecularly engineered dye aggregates have allowed for the design and control of simple one-dimensional structures and closed structures. In this study, a new dyad was introduced that can form nanotoroids, nanotubes, or 1D fibers depending on the conditions. This is the first successful example of light-induced modulation of supramolecular polymorphism to produce distinctly nanostructured aggregates under isothermal conditions.
Article
Chemistry, Multidisciplinary
Natsuki Suda, Hironari Arima, Takuho Saito, Takumi Aizawa, Shiki Yagai
Summary: A scissor-shaped foldable diphenylanthracene dyad has been synthesized to self-assemble into elongated thin nanofibers in a nonpolar solvent, exhibiting intense blue emission. Efficient gelation was observed at millimolar concentration while maintaining the emission property in the gel state.
Article
Chemistry, Multidisciplinary
Sho Takahashi, Shiki Yagai
Summary: This study demonstrates an example of thermodynamically controlled random supramolecular copolymerization. By forming six-membered hydrogen-bonded rosette intermediates, the random copolymerization of two monomers with distinct molecular structures is achieved. The experimental results reveal the homopolymerization of one monomer in the high-temperature region and the incorporation of the other monomer in the medium-temperature region to form supramolecular copolymers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Chi Feng, Tomohiro Seki, Shunichi Sakamoto, Toshiyuki Sasaki, Satoshi Takamizawa, Hajime Ito
Summary: This study discovered a reversible multi-stage shape-changing effect in a molecular crystal, where the shape changes and luminescence-color changes were induced by multi-step thermal phase transitions. The findings provide new strategies for imparting additional functionalities to known shape-memory materials.
Article
Chemistry, Multidisciplinary
Takumi Aizawa, Maika Kawaura, Takashi Kajitani, Kowit Hengphasatporn, Yasuteru Shigeta, Shiki Yagai
Summary: This study reports the self-assembly of 2-thiobarbituric acid-functionalized naphthalene dye into crystalline fibers, which exhibit different material properties compared to the previously reported oxo-barbituric acid derivative that forms curved supramolecular polymers. Detailed analysis using H-1-NMR, DFT calculation, and X-ray diffraction reveals that the crystalline fiber is formed through a tape-like hydrogen-bonding pattern due to the weaker hydrogen-bond-acceptor ability of the thiocarbonyl group.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Sougata Datta, Sho Takahashi, Shiki Yagai
Summary: Recently, supramolecular polymers (SPs) have gained attention as a class of materials that can overcome the potential environmental problems of conventional polymeric materials. The development of various supramolecular polymers is important not only for their direct application as materials but also because their unique polymerization processes and dynamic properties have a profound influence on the development of polymeric and small-molecule-based functional materials. By limiting the dimensionality of molecular assemblies to one dimension, essential aspects of self-assembly and self-organization can be discovered. Curved supramolecular polymers (CSPs) have been studied to understand the major features of polymer chains when intrinsic structural order generates curvature. The use of one-dimensional stacked supramolecular polymers allows for free control of structure at the single-polymer-chain level.
ACCOUNTS OF MATERIALS RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Kenta Tamaki, Takumi Aizawa, Shiki Yagai
Summary: The barbiturate-functionalized supramolecular monomer with an ester-linked biphenyl and azobenzene pi-conjugated core produces wavy supramolecular polymers, with the periodic inversion of curvature attributed to the conformational rigidity of the monomer and repulsive interactions between rosettes. Furthermore, photoisomerization of the azobenzene moiety increases the fragility of the main chain without compromising its periodic structure.
CHEMICAL COMMUNICATIONS
(2021)
