Article
Chemistry, Multidisciplinary
Naoyuki Hisano, Tomoki Kodama, Takeharu Haino
Summary: The negative homotropic allostery of a triple-layered trisporphyrin cleft with two guest binding sites is confirmed. The trisporphyrin can accommodate two guest molecules within the cleft through pi-pi stacking and donor-acceptor interactions. The binding of the first guest by the trisporphyrin incurs an enthalpy penalty that weakens the successive binding process, as revealed by experimental and computational studies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Multidisciplinary
Naoyuki Hisano, Tomoki Kodama, Takeharu Haino
Summary: This article features the group of Takeharu Haino at Hiroshima University on the cover. The image illustrates a host-guest complex of a trisporphyrin double cleft with an electron-deficient aromatic molecule, demonstrating negative cooperativity in guest binding. The full article can be read at 10.1002/chem.202300107.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Ina Heckelmann, Zifei Lu, Joseph C. A. Prentice, Florian Auras, Tanya K. Ronson, Richard H. Friend, Jonathan R. Nitschke, Sascha Feldmann
Summary: We report the self-assembly of a supramolecular pseudo-cube formed from six perylene diimides (PDIs), which suppresses aggregation and allows for non-aggregated, monomer-like properties. The stabilized excited state in the cage enables delayed fluorescence, acting as an excited-state reservoir. This self-assembly technique provides a powerful tool for controlling the electronic properties of chromophores and advancing molecular electronics devices.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Christopher J. Kingsbury, Marc Kielmann, Brendan Twamley, Mathias O. Senge
Summary: Coordinating the spatial arrangement of electroactive partners is crucial in designing molecular electronics and photonics. This study demonstrates a viable method of organizing electroactive centers into filaments and monolayers by manipulating nonplanar porphyrins through self-organization and charge-balance principles. The results provide insights into the interactions and induced conformations of porphyrin acids and nonstandard counterions, facilitating the development of surface deposition and ultrathin devices.
Article
Chemistry, Inorganic & Nuclear
Susana Ibanez, Eduardo Peris
Summary: Two different metallotweezers were used as hosts for a series of planar aromatic guests. The binding strength and models of the two metallotweezers differed due to their structural differences.
INORGANIC CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Manuela Stefanelli, Gabriele Magna, Corrado Di Natale, Roberto Paolesse, Donato Monti
Summary: Conjugating the porphyrin ring with an amino acid via amide linkage allows for the creation of both amphiphilicity and chirality in the macrocycle. The use of proline residue is advantageous due to its conformational rigidity, which allows for efficient transfer and amplification of molecular chirality in aqueous environments. This article describes the evolution of studies conducted by the authors to achieve chiral systems from porphyrin-proline derivatives, both in solution and in the solid state. The discussion focuses on fundamental aspects that influence the resulting molecular architectures, including the nature of the appended group, the presence of coordinated metal ions, and the properties of the solvent. The fine-tuning of these parameters enables the creation of stereospecific structures with distinct chiroptical and morphological features. Solid films based on these chiral systems are also obtained and their recognition abilities in gaseous and liquid phases are discussed.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Multidisciplinary
Kentaro Harada, Ryo Sekiya, Takeharu Haino
Summary: By utilizing a confined space, we have achieved the formation of trimeric structures composed of acetic acid and tartaric acid derivatives, with transfer and enrichment of chirality. The generated capsule guides the dynamic axial chirality and enables the emission of circularly polarized luminescence in the NIR region.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Courtney Ngai, Hoi-Ting Wu, Bryce Camara, Christopher G. Williams, Leonard J. Mueller, Ryan R. Julian, Richard J. Hooley
Summary: A self-assembled cage structure was synthesized by controlling the self-assembly of internal amines. Despite carrying a positive charge, the structure can extract protons from water in solution. The internal amines have lower basicity compared to their counterparts in free solution. This moderation is a hallmark of enzymatic catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Zhi-Yuan Zhang, Chunju Li
Summary: Macrocyclic compounds are important tools in supramolecular chemistry, but traditional macrocycles have limitations in accommodating large molecules or structures. We have developed a versatile and modular strategy for synthesizing a new family of macrocycles, biphen[n]arenes, with customizable cavity sizes and diverse backbones. These biphen[n]arenes exhibited interesting recognition properties and self-assembly abilities, showing potential applications in various fields.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Li Shao, Hanwen Zhang, Xiaoqing He, Bin Hua, Xiangquan Hu, Caixia Wan, Steven P. Kelley, Jerry L. Atwood
Summary: A novel host-guest recognition motif based on PgC(3) and PEG was reported, which can selectively entrap high molecular weight PEG to form complex structures, and PgC(3) has the ability to efficiently adsorb PEG from aqueous solutions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
B. Hua, L. O. Alimi, G. Zhang, Y. Ding, B. Moosa, W. S. Baslyman, N. M. Khashab
Summary: This study investigates the use of methylene-bridged trianglamines as supramolecular adsorbents for the selective separation of linear alkane isomers. The selectivity is attributed to the host-guest complexation resulting from the size matching between the trianglamines cavity and the linear guest molecules. Moreover, the supramolecular adsorbents exhibit high recyclability and almost no loss of efficiency, showing great promise for industrial applications.
MATERIALS TODAY CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Chiara F. M. Mirabella, Gemma Aragay, Pablo Ballester
Summary: We report the self-assembly of shape-persistent [1 + 1] tetra-imine cages 1 based on two different tetra-alpha aryl-extended calix[4]pyrrole scaffolds in chlorinated solvents and in a 9 : 1 CDCl3 : CD3CN solvent mixture. The use of a bis-N-oxide 4 as template has a positive effect on the reaction yield. The binding properties of the self-assembled tetra-imine cages 1 with pyridine N-oxide derivatives were investigated using H-1 NMR spectroscopy.
Article
Nanoscience & Nanotechnology
Kui Wang, Si-Chen Liu, Guo-Jie Gao, Siyang Xing, Bolin Zhu
Summary: In this study, the coordination effects of protoporphyrin IX disodium salt (PpIX) with Cu-II, Fe-II, and Zn-II were investigated, along with the host-guest interactions of calixpyridinium with PpIX and the three metalloporphyrins. The bonding ratio between calixpyridinium and PpIX differed from that with the other metalloporphyrins due to the reduction of the electronegativity of PpIX caused by the coordination of metal cations. Moreover, the supramolecular nanoassemblies formed by the host-guest interactions exhibited a reversible temperature responsiveness, allowing for reversible fluorescence on-off control and potential application as an intelligent light-responsive fluorescent security ink.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Niklas Grabicki, Sergey Fisher, Oliver Dumele
Summary: Researchers synthesized an ethylene glycol-decorated [6]cyclo-meta-phenylene (CMP) macrocycle, which was used as a subunit to construct a fourfold Au-2(I)-aryl metallacycle with a square arrangement. The corners of the metallacycle consisted of rigid dinuclear gold(I) complexes, which were previously known to form only triangular metallacycles. The conformational flexibility of the [6]CMP macrocycle and the rigid dinuclear gold(I) moieties allowed for the square geometry, as confirmed by single-crystal X-ray diffraction. The gold complex formation showed size-selectivity compared to an alternative route using platinum(II) corner motifs. Upon reductive elimination, an all-organic ether-decorated carbon nanoring was obtained. Investigation as a host for the complexation of large guest molecules with suitable convex pi-surfaces was conducted using isothermal NMR binding titrations, and association constants for [6]cycloparaphenylene ([6]CPP), [7]CPP, C-60, and C-70 were determined.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Natsumi Nitta, Shin-ichi Kihara, Takeharu Haino
Summary: We developed a new synthetic method to construct supramolecular A(8)B(n) (n=1, 2, 4) miktoarm star copolymers through host-guest complexation. The formation of these copolymers was confirmed by various analytical techniques. The miktoarm copolymers exhibited phase separation in bulk, and the micro-Brownian motion of the A(8)B(4) structure was enhanced due to weak segregation interaction between immiscible arms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
