Article
Chemistry, Multidisciplinary
Pengfei Wu, Adriana Pietropaolo, Mariagrazia Fortino, Masayoshi Bando, Katsuhiro Maeda, Tatsuya Nishimura, Shuhei Shimoda, Hiroyasu Sato, Naofumi Naga, Tamaki Nakano
Summary: Optically active polymers with neomenthyl and pentyl groups were used as host polymers to efficiently include different chirality acceptors. Chirality transfer was more efficient with higher-molar-mass and hyperbranched polymers. Included molecules may exhibit ordered intermolecular arrangement and exhibit efficient circularly polarized luminescence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Giovanni Preda, Sebastian Jung, Gennaro Pescitelli, Lorenzo Cupellini, Dominique Armspach, Dario Pasini
Summary: Chiroptical materials are gaining increasing interest due to their innovative character and applications. This study presents the synthesis and characterization of a two-level molecular stack combining a chiral cyclodextrin element and an axially chiral biphenyl element, capable of effectively translating the stereochemical information and exhibiting stimuli-responsive chiroptical properties. The chiroptical properties can be finely tuned by external stimuli.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Michael Kemper, Sven Reese, Elric Engelage, Christian Merten
Summary: The stabilization of chiral propeller conformations in triaryl compounds is challenging due to low racemization barriers. However, the incorporation of point-chiral alkylether chains and subsequent locking of the structure with ammonia can induce chiral conformational preferences in triaryl boranes. A four-point interaction involving Lewis-adduct formation and three hydrogen bonds was proposed as the stabilizing mechanism. DFT calculations predicted no significant preference for propeller handedness, but vibrational circular dichroism spectroscopy revealed a measurable excess of one propeller handedness. The steric demand of the amine was found to play a key role in the induction process and preventing blade rotations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Aleksandra Kolodziejczyk, Laurence A. Nafie, Aleksandra Wajda, Agnieszka Kaczor
Summary: Amyloid fibrils exhibit multi-layered chiral supramolecular structures and are highly sensitive to vibrational circular dichroism (VCD) for fibril formation. In this study, we demonstrate an exceptionally large enhancement of Raman optical activity (ROA) signal in mature amyloid fibrils and their prefibrillar states. This enhanced ROA signal is observed in fibrils of different proteins, indicating a possible general phenomenon. The ROA signal appears earlier than VCD and provides access to a broader range of vibrations, suggesting its potential utility for analyzing amyloid fibrils.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Julian Full, Santosh P. Panchal, Julian Gotz, Ana-Maria Krause, Agnieszka Nowak-Krol
Summary: Helically chiral compounds with one and two boron atoms were synthesized using a modular approach, showing exceptional configurational stability and fluorescence properties. The compounds are proposed as primary structures of extended helices, with potential applications in materials science.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Physics, Applied
Yilin Wang, Weijin Chen, Shilei Li, Zhi-Ling Hou, Li Yu
Summary: The extrinsic chiroptical effects based on directional nanoantennas are explored in this study. These effects are characterized by the angular emission patterns in momentum space, and can be tuned by changing the refractive index of the surrounding medium. This research provides a new perspective for understanding chirality and has important applications in biosensing and chiral photon detection.
JOURNAL OF APPLIED PHYSICS
(2022)
Review
Chemistry, Multidisciplinary
Federico Begato, Giulia Licini, Cristiano Zonta
Summary: Spatial organization using confinement has been extensively studied in the field of supramolecular chemistry, with applications in sensing, catalysis, and delivery continuously emerging. This minireview focuses on the applications of chiral supramolecular cages (CSC) in catalysis, sensing, and chiroptical properties. The review discusses the preparation strategies for chiral supramolecular cages, including both purely organic architectures and those prepared using metal-ligand coordination bonds. Recent findings on the applications of CSC, particularly in stereodynamic systems, are presented to highlight the current scientific interests and future opportunities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Medicinal
Francesco Bertocchi, Cristina Sissa, Anna Painelli
Summary: In this tutorial, we present two alternative methods for calculating the circular dichroism (CD) spectra of non-chiral chromophores in chiral supramolecular assemblies. Despite their apparent differences, these two approaches are based on the same underlying approximations, and are expected to yield similar results. By providing explicit analytical expressions for the CD responses of a dimer in both approaches, we demonstrate their perfect equivalence. Numerical results for larger systems further validate this outcome. This tutorial aims to provide young students and scientists entering the field with a useful introduction to the fascinating topic of supramolecular chirality.
Review
Chemistry, Physical
Qianwei Liu, Bixin Jin, Qin Li, Huanzhi Yang, Yunjun Luo, Xiaoyu Li
Summary: Self-assembly is a common phenomenon in living systems, and scientists have been trying to emulate its intricacy, homogeneity, and versatility in artificial building blocks. Self-sorting assembly in multicomponent systems allows for the spontaneous recognition and spatial aggregation of the same or interactive building units, leading to well-ordered products or hierarchical structures in a one-step manner. This efficient assembly strategy has attracted significant research attention, particularly in artificial systems using supramolecular and polymeric building blocks.
Article
Biochemistry & Molecular Biology
Ilaria Tomei, Beatrice Bonanni, Anna Sgarlata, Massimo Fanfoni, Roberto Martini, Ilaria Di Filippo, Gabriele Magna, Manuela Stefanelli, Donato Monti, Roberto Paolesse, Claudio Goletti
Summary: Reflectance anisotropy spectroscopy (RAS) is widely used in the investigation of organic compounds, especially porphyrins and porphyrin-related compounds, due to its unique characteristics. The CD-RAS technique, which measures the circular dichroism of samples, allows for the study of the anisotropy of the optical properties under circularly polarized light. The open structure and flexibility of this new spectrometer make it suitable for coupling with UHV systems or other experimental configurations. In this manuscript, the CD-RAS technique is detailed and calibration tests with chiral porphyrin assemblies are reported to validate the results obtained using a commercial spectrometer.
Review
Multidisciplinary Sciences
Takashiro Akitsu, Sanyobi Kim, Daisuke Nakane
Summary: The study explored the supramolecular chirality induced by circularly polarized light and the potential impact of optical vortex light on photochemical materials. The research focused on the differences in spin angular momentum and orbital angular momentum depending on molecular orientation in polymer films. The preliminary theoretical results indicated that UV light under vortex can cause trans-cis photoisomerization of azo dyes, affecting the CD spectra of the molecules.
Article
Chemistry, Multidisciplinary
Gianluigi Albano, Francesco Zinna, Francesco Urraci, Maria Annunziata M. Capozzi, Gennaro Pescitelli, Angela Punzi, Lorenzo Di Bari, Gianluca M. Farinola
Summary: This study investigates the chiroptical features of chiral DPP derivatives and reveals the superior capability of ECD spectroscopy compared to absorbance spectroscopy in detecting aggregation modes and multiple pathways.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Marius Morgenroth, Mirko Scholz, Laure Guy, Kawon Oum, Thomas Lenzer
Summary: We have observed efficient induction of chirality in polyfluorene copolymer thin films by mixing with helicene-type chiral additives based on the dibenzo[c,h]acridine motif. Circular dichroism (CD) and circularly polarized luminescence (CPL) microscopy provide information about the chiral arrangements in the thin films. The CD signal shows a characteristic dependence on the film thickness, supporting a supramolecular origin of the strong chiral response.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Semih Sevim, Alessandro Sorrenti, Joao Pedro Vale, Zoubir El-Hachemi, Salvador Pane, Andreas D. Flouris, Tiago Sotto Mayor, Josep Puigmarti-Luis
Summary: This article presents an example of chirality transfer from the chiral shape of a 3D helical channel to chiral supramolecular aggregates, where the handedness of the helical channel determines the direction of enantioselection. By combining numerical simulations and experimental data, the authors demonstrate the possibility of controlling enantioselectively molecular processes at the nanometer scale by modulating the geometry and operating conditions of fluidic reactors.
NATURE COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Shoma Hirokawa, Nagao Kobayashi, Soji Shimizu
Summary: The study elaborates inherently chiral subporphyrins by forming a fused pyran ring at the periphery, showing that the chiroptical properties can be controlled by peripheral substitution and meso-aryl substituents. The circular dichroism (CD) properties of chiral subporphyrins are largely affected by the peripheral substituents and the dihedral angles between the meso-aryl substituents and the subporphyrin core.
Article
Chemistry, Multidisciplinary
Evanie Franz, Daniel Krappmann, Lukas Fromm, Tobias Luchs, Andreas Goerling, Andreas Hirsch, Olaf Brummel, Joerg Libuda
Summary: This study investigated the influence of molecular design on the electrochemically triggered back-conversion reaction in MOST systems for the first time, showing that the electrochemical stability of a NBD/QC couple can be easily tuned by simple structural changes. Furthermore, the low charge input and current for the electrochemically triggered energy release ensure a high overall efficiency of the MOST system.
Article
Chemistry, Multidisciplinary
Sabrin Al-Fogra, Bowen Yang, Lisa Jurkiewicz, Frank Hauke, Andreas Hirsch, Tao Wei
Summary: This study presents a facile and universal laser writing approach for covalent patterning of graphene, leading to the formation of graphene architectures consisting of antaratopically functionalized superlattices, which were previously elusive.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Andreas Eigen, Lisa M. S. Stiegler, Susanne Gradl, Vanessa Schneider, Vincent Wedler, Henrik Gass, Lukas Mueller, Marco Sarcletti, Markus R. Heinrich, Andreas Hirsch, Marcus Halik
Summary: The formation of mixed shell-by-shell systems with tunable compositions is demonstrated by using molecular self-assembly driven by chemical recognition motifs. By using aluminum oxide nanoparticles as template surfaces, the composition of the shell-by-shell assemblies can be controlled. The composition of the assemblies is studied and vesicle-like bilayer structures can be formed.
ADVANCED MATERIALS INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Markus Freiberger, Martin B. Minameyer, Iris Solymosi, Stefan Fruehwald, Marcel Krug, Youzhi Xu, Andreas Hirsch, Timothy Clark, Dirk M. Guldi, Max von Delius, Konstantin Amsharov, Andreas Goerling, M. Eugenia Perez-Ojeda, Thomas Drewello
Summary: We studied the gas-phase chemistry of [10]cycloparaphenylene ([10]CPP) non-covalent complexes with C-60 and C-70 using atmospheric pressure photoionization and electrospray ionization mass spectrometry. The stability and charge distribution of these complexes were analyzed using energy-resolved collision-induced dissociation (ER-CID). It was found that complexes with a C-70 core exhibited greater stability, and the radical cations were more stable than the radical anions. [2:1] complexes of the ([10]CPP2 superset of C-60/70)(+center dot/-center dot) type were observed as isolated solitary gas-phase species for the first time. The stability of these complexes was reduced compared to the [1:1] complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Johannes Muller, Janina Buck, Andreas Hirsch
Summary: This paper presents nine pi-expanded mono-substituted 5,8,11,14,17-pentakis-(tert-butyl)-hexa-peri-hexabenzocoronenes (HBC) and explores their synthesis method and the influence of substitution groups on their optoelectronic properties.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Laura von Lueders, Rita Tilmann, Kangho Lee, Cian Bartlam, Tanja Stimpel-Lindner, Tarja K. Nevanen, Kristiina Iljin, Kathrin C. Knirsch, Andreas Hirsch, Georg S. Duesberg
Summary: We present a controllable and specific functionalisation approach for graphene field-effect transistors (GFETs) in order to detect small physiologically active molecules. The key step involves the noncovalent functionalisation of graphene with perylene bisimide (PBI) molecules directly on the growth substrate. This method allows for the homogeneous self-assembly of PBI molecules on graphene, followed by the immobilization of antibodies. The functionalised GFET devices showed excellent performance in terms of atomic force microscopy, Raman spectroscopy, and electrical measurements compared to conventional functionalisation methods. Specific sensing of small molecules such as methamphetamine and cortisol was achieved by monitoring the electrical changes of the functionalised GFET devices. The sensors were able to detect methamphetamine down to a concentration of 300 ng ml(-1).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Felix Hemauer, Valentin Schwaab, Eva Marie Freiberger, Natalie J. Waleska, Andreas Leng, Cornelius Weiss, Johann Steinhauer, Fabian Duell, Philipp Bachmann, Andreas Hirsch, Hans-Peter Steinrueck, Christian Papp
Summary: This study investigates the surface chemistry of a derivatized norbornadiene/quadricyclane molecule pair and explores their potential as energy storage solutions for renewable energy sources. It demonstrates the success of triggering the release of stored energy on Pt(111) and reveals the decomposition pathways of the two isomers on Ni(111).
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jovana Jaksic, Iris Solymosi, Andreas Hirsch, M. Eugenia Perez-Ojeda, Aleksandra Mitrovic, Veselin Maslak
Summary: This study presents the synthesis and characterization of four dumbbell-shaped fullerene molecules connected by isosorbide and isomannide moieties. The electrochemical behavior of these molecules and their ability to form complexes with [10]cycloparaphenylene ([10]CPP) were investigated. The results showed a high electron affinity for the fullerene dumbbells, indicating a strong interaction with carbon nanorings.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Sven Moersel, Rene Kellner, Andreas Hirsch
Summary: The synthesis of novel fluorinated hexa-peri-hexabenzocoronenes (HBCs) and their thioether-substituted analogs was reported, with the reaction time significantly reduced by using microwave assistance. Increasing fluorination or thioether-substituents led to a decrease in the extinction coefficient of the HBCs. Addition of thioether-moieties caused a shift in absorption and emission bands, while the nature of the thioether did not affect the optoelectronic properties. Oxidation to sulfone and formation of sulfonium salts further modified the electronic environment of the HBC core, resulting in decreased extinction coefficients and broadening of absorption and emission bands.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(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
Nanoscience & Nanotechnology
Maria Kolesnik-Gray, Laura Meingast, Martin Siebert, Tim Unbehaun, Tobias Huf, Guenter Ellrott, Gonzalo Abellan, Stefan Wild, Vicent Lloret, Udo Mundloch, Julian Schwarz, Michael Niebauer, Maximilian Szabo, Mathias Rommel, Andreas Hutzler, Frank Hauke, Andreas Hirsch, Vojislav Krstic
Summary: In this work, the DC electrical transport characteristics of high-quality black phosphorus (BP) field-effect devices with different thicknesses were studied at room temperature. The experimental data showed that the conductivity and hole density increase non-trivially with a reduced number of layers while maintaining constant field-effect mobility due to electron-phonon scattering. The observed phenomena were found to be a direct consequence of significant interlayer coupling, resulting in a local redistribution of free charge carriers towards the central layers. It was also discovered that a naturally protected 2D hole gas can be encapsulated in BP flakes as thick as 10 nm due to the electrostatic environment.
NPJ 2D MATERIALS AND APPLICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Juan S. S. Rocha-Ortiz, Jianchang C. Wu, Jonas Wenzel, Andreas J. J. Bornschlegl, Jose Dario Perea, Salvador Leon, Anastasia Barabash, Anna-Sophie Wollny, Dirk M. M. Guldi, Jiyun Zhang, Alberto Insuasty, Larry Lueer, Alejandro Ortiz, Andreas Hirsch, Christoph J. J. Brabec
Summary: Dumbbell-shaped systems based on PAHs-BODIPY-triarylamine hybrids TM-(01-04) are designed and employed as hole-transporting materials in planar inverted perovskite solar cells, exhibiting remarkable stability and high power conversion efficiency. The conjugated pi-system's covalent attachment and size are found to influence the energy transfer within the systems. Integrating these systems into the solar cells results in outstanding power conversion efficiency, with TM-02-based devices achieving a PCE of 20.26%. The long-term stability of these devices is also measured, with TM-04-based device showing the highest stability of 94%.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Applied
Juan S. Rocha-Ortiz, Joel Jose Montalvo-Acosta, Yakun He, Alberto Insuasty, Andreas Hirsch, Christoph J. Brabec, Alejandro Ortiz
Summary: Eight novel C60-BODIPY-Triarylamine electroactive triads were synthesized and characterized, and the effect of different linkers and functionalization on the electronic properties were studied. The compounds showed strong absorption of visible light and photo-induced electron transfer, confirmed by solvatochromic effects and redox potentials. The study also found that the pyrrolidine derivatives were more stable than isoxazoline analogs and alkoxy units improved thermal endurance.
Article
Chemistry, Multidisciplinary
Markus Freiberger, Iris Solymosi, Eva Marie Freiberger, Andreas Hirsch, M. Eugenia Perez-Ojeda, Thomas Drewello
Summary: In this study, the stability of [n]cycloparaphenylene (nCPP)-based host-guest complexes with Li+@C-60 and C-60 was compared for the first time in both gas and solution phases. Results showed a significant increase in stability for the complexes featuring [9-12]CPP with Li+@C-60, which was also observed in solution. The formation of [10]CPP superset of Li+@C-60 exhibited a two orders of magnitude larger association constant compared to the C-60 analog, along with an increased binding entropy. This research contributes to a better understanding of host-guest complexes between [n]CPPs and endohedral metallofullerenes at a molecular level.
Article
Chemistry, Multidisciplinary
Wiebke Zika, Andreas Hirsch, Rene Weiss, Simone Pinter, Christoph M. Schuesslbauer, Timothy Clark, Andreas Hirsch, Dirk M. Guldi
Summary: This study investigates the interconversion between QC and NBD and their application in energy storage through photo-assays. An oxidative electron transfer is observed during the QC-to-NBD isomerization using transient absorption spectroscopy. The complementary use of time-resolved and steady-state spectroscopies allows for a complete description of the photoisomerization reaction of NBDs.
