Article
Chemistry, Multidisciplinary
Arkadiusz Marek Sakowicz, Agnieszka Szumna
Summary: This study presents the synthesis of new chiral water-soluble dimeric capsules using the multicomponent Mannich reaction and subsequent self-assembly. These capsules are capable of effectively encapsulating a variety of chiral molecules with mixed polar/apolar characters. The formation of heterocapsules using additional interactions between charged acidic and basic side chains leads to improved encapsulation properties.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jorge Labella, Deb Kumar Bhowmick, Anil Kumar, Ron Naaman, Tomas Torres
Summary: High spin polarization (SP) in studies of chiral induced spin selectivity (CISS) is achieved through proper organization of chiral molecules using anchoring groups or complex supramolecular polymers. A new class of spin filters based on bowl-shaped aromatics show high-quality thin-film formation through simple spin-coating and exhibit high spin filtering properties. Devices containing enantiopure tribromo-subphthalocyanines (SubPcs) demonstrate well-ordered chiral structures and achieve high SPs comparable to current complex methodologies, opening up new possibilities for realistic and efficient spintronic devices based on the CISS effect.
Article
Chemistry, Multidisciplinary
Aaron D. W. Kennedy, Ray G. DiNardi, Lucy L. Fillbrook, William A. Donald, Jonathon E. Beves
Summary: A study has shown that a photoswitchable ligand and palladium(II) ions can form dynamic metallosupramolecular structures. By irradiating with light, the distribution of isomers in the ligand can be controlled, resulting in selective disassembly and formation of stable structures. This approach provides a new strategy for reversible control of self-assembled structures.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Qingsong Xu, Chunyang Yu, Lingsheng Jiang, Yuling Wang, Feng Liu, Wenfeng Jiang, Yongfeng Zhou
Summary: Hierarchical bishell capsules (BCs) with ultrathin lamellar phases have been prepared through a coacervate-assisted polymerization-induced self-assembly (CAPISA) method, which combines liquid-liquid phase separation (LLPS) with polymerization-induced self-assembly (PISA). The CAPISA method allows for the one-pot and scalable preparation of BCs in a bottom-up sequence, and the self-assembled structure and dynamic formation process of BCs have been revealed. CAPISA shows great potential in fabricating biomimetic polymer materials with higher structural complexity and sophisticated functions.
Article
Chemistry, Organic
Xinyi Ren, Lin Tang, Chaoren Shen, Huimin Li, Peng Wang, Kaiwu Dong
Summary: A palladium-catalyzed asymmetric hydroesterification-cyclization method was developed for efficient preparation of enantioenriched gamma-lactams, with good selectivities and a broad substrate scope. The correlation between multiple selectivities and N-substitutes of the amide linker in the substrate was demonstrated through crystallographic evidence and control experiments.
Article
Chemistry, Inorganic & Nuclear
Jan Holub, Antonio Santoro, Mihail-Adrian Stadler, Jean-Marie Lehn
Summary: The sequential assembly of terminally functionalized bishydrazone ligands followed by coordination with Zn(ii) metal cations yields multi-functionalized grid-type complexes. The introduction of aldehyde functional groups results in octavalent grids, offering potential for diverse dynamic covalent decorations. Further connection with a difunctional covalent linker leads to folded molecular grids with double hairpins geometry, allowing for multifunctional dynamic covalent chemistry.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Roan A. S. Vasdev, James A. Findlay, David R. Turner, James D. Crowley
Summary: A new ferrocene-containing self-assembled double-walled triangle structure has been synthesized and characterized, showing interactions with anionic guest and redox activity without influence from the guest.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Antonino Cucinotta, Christophe Kahlfuss, Andrea Minoia, Samuel Eyley, Keanu Zwaenepoel, Gangamallaiah Velpula, Wim Thielemans, Roberto Lazzaroni, Veronique Bulach, Mir Wais Hosseini, Kunal S. Mali, Steven De Feyter
Summary: In this study, we achieved the expression and amplification of chirality in 2D metallosupramolecular networks formed by a nucleobase derivative. A racemic compound was obtained in the absence of coordinating metal ions, but spontaneous resolution occurred upon the addition of a coordinating ion or suitable guest molecule. The use of enantiopure solvent broke the mirror symmetry and resulted in a globally homochiral surface.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Francisco Rey- Tarrio, Emilio Quinoa, Gustavo Fernandez, Felix Freire
Summary: A unique multi-helical material combining information from metallosupramolecular and covalent helical polymers is presented. The helical structure of the poly(acetylene) backbone guides the pendant groups in a way that generates a tilting degree and forms a multi-chiral material.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Christophe Gourlaouen, Fethi Elaieb, Eric Brenner, Dominique Matt, Jack Harrowfield, Louis Ricard
Summary: This study investigated the conformational preference of a cavity-based biaryl phosphine, 5-(2-diphenylphosphinyl-phenyl)-25,26,27,28-tetrapropyloxycalix[4]arene (L), through density functional theory calculations. The analysis revealed that the rotation barrier of the biaryl unit around the C-C axis is only 10.7 kcal mol(-1), allowing the existence of two types of conformers: one with the P lone pair inside the cavity pointing to the calixarene interior, and the other with a more open structure where the P atom is located outside the cavity. Single crystal X-ray diffraction study showed that the biaryl phosphine is essentially an atropisomer in the solid state, with the phosphorus atom completely out of the cavity defined by the four phenoxy rings.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Ehsan Raee, Bingqing Liu, Yuqing Yang, Trishool Namani, Yunpeng Cui, Nita Sahai, Xiaopeng Li, Tianbo Liu
Summary: This study reveals that the self-assembly of chiral Pd12L24 metal-organic cages can be influenced by the size of the amino acid side group used as the chiral counterion. Bulkier side groups can erase chiral discrimination, while smaller side groups result in chiral discrimination.
Article
Chemistry, Inorganic & Nuclear
Hong-Lin Lu, Jin Tong, Xiao-Peng Hu, Wei Deng, Shu-Yan Yu
Summary: A series of capsule-like anion receptors were successfully self-assembled by coordinating flexible amide based polypyrazole ligands with dipalladium corners in aqueous solution. Characterization of these complexes using various techniques confirmed their ability to unsymmetrically accommodate nitrate anions via hydrogen bonding and other weak interactions. NMR titrations in dimethyl sulfoxide showed high selectivity of complexes 1 and 2 for encapsulating nitrate ions.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Takashi Mino, Yohei Fujisawa, Shizuki Yoshida, Mitsuru Hirama, Takumu Akiyama, Ryo Saito, Yasushi Yoshida, Yoshio Kasashima, Masami Sakamoto
Summary: By synthesizing cinnamoyl amide type chiral P,olefin ligand (S)-4, separable diastereomers of 4d were obtained successfully, and asymmetric allylic substitution reactions of indoles using (S,aS)-4d as a chiral ligand demonstrated high enantioselectivities (up to 98% ee).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhongxin Li, Lei Zhang, Qinghua Wu, Heng Li, Zhengxin Kang, Changjiang Yu, Erhong Hao, Lijuan Jiao
Summary: A new class of hybridized and core-contracted porphyrinoids with intense absorption and emission properties has been reported, and their stability and photostability make them a subject of extensive research.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Shuguo An, Aiyou Hao, Pengyao Xing
Summary: This study reports the first example of polyhedral oligosilsesquioxane (POSS) derivatives that can self-assemble into well-defined chiral nanoassemblies. These chiral nanoassemblies exhibit active chiroptical responses and can bind guest molecules through charge-transfer interactions, offering a new design protocol for functional chiral materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Benedikt Platzer, Basma Ghazal, Victor Marinas, Jorge Labella, M. Victoria Martinez-Diaz, Saad Maksheed, Dirk M. Guldi, Tomas Torres
Summary: This study reports the synthesis and photophysical characterization of a ZnPc-SubPc conjugate connected through a short-range alkyne spacer, confirming the occurrence of complete charge separation from a photoexcited charge transfer state.
Review
Chemistry, Multidisciplinary
Nedjeljko Seselj, Silvia M. M. Alfaro, Eftychia Bompolaki, Lars N. N. Cleemann, Tomas Torres, Kobra Azizi
Summary: The constant increase in global emission standards has led to the importance of fuel cell (FC) technology. Research in the past two decades has focused on developing more active catalysts for high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC) and improving their durability. Two main approaches have been suggested: alloying platinum (Pt) with low-cost transition metals to reduce Pt usage, and developing novel catalyst supports to enhance metal particle anchoring and inhibit corrosion phenomena. This comprehensive review details the recent development of platinum group metal (PGM) and platinum group metal free (PGM-free) catalysts, as well as alternative carbon (C) supports for HT-PEMFCs.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Marta Gomez-Gomez, Jorge Labella, Tomas Torres
Summary: This study presents the synthesis, electronic properties, and reactivity of borylated subphthalocyanines, which are prepared via Suzuki-Miyaura borylation with high yields. These compounds are easily purified, exhibit excellent stability, and serve as powerful starting materials for post-functionalization of SubPcs. This novel approach is more efficient than existing methods and enables the preparation of exotic SubPc dimeric species with promising properties for optoelectronic devices.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Medicinal
Gonzalo Duran-Sampedro, Evelyn Y. Xue, Marta Moreno-Simoni, Celia Paramio, Tomas Torres, Dennis K. P. Ng, Gema de la Torre
Summary: Pt(II)-BODIPY complexes combine the chemotherapeutic activity of Pt(II) with the photocytotoxicity of BODIPYs. Additional conjugation with targeting ligands can boost the uptake by cancer cells that overexpress the corresponding receptors. Both Pt(II) triangles, 1 and 2, built with pyridyl BODIPYs functionalized with glucose or triethylene glycol methyl ether, showed higher singlet oxygen quantum yields and cellular uptake compared to non-functionalized BODIPYs.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Henrik Gotfredsen, Dominik Thiel, Phillip M. Greibel, Lan Chen, Marcel Krug, Ilias Papadopoulos, Michael J. Ferguson, Mogens Brondsted Nielsen, Tomas Torres, Timothy Clark, Dirk M. Guldi, Rik R. Tykwinski
Summary: This study investigates the influence of sensitizer-chromophore geometry on the separation of singlet excited states into triplet excited states. Two conjugates with different arrangements were synthesized and compared. The results show that the energy transfer rate is 26 times faster in the peripheral arrangement, even though the chromophores are farther apart. This rate acceleration is attributed to the more favorable relative orientation of the transition dipole moments in the peripheral structure. These findings are of significant importance for solar energy research.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Jorge Labella, Tomas Torres
Summary: Subphthalocyanines (SubPcs) have been extensively researched due to their unique properties, rich chemistry, and wide applicability. Significant progress has been made in understanding the molecular structure-property relationship of SubPcs and implementing them in advanced technological devices. However, SubPcs still have untapped potential more than 50 years after their discovery. In this short review, we highlight the main trends in SubPc chemistry, with a focus on their use as molecular materials.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ainhoa Salazar, Marta Moreno-Simoni, Sunit Kumar, Jorge Labella, Tomas Torres, Gema de la Torre
Summary: This study introduces a supramolecular cage that acts as a catalytic molecular reactor for transformations over fullerenes in aqueous medium. The cage, based on metallo-organic Pd(II)-subphthalocyanine, facilitates Diels-Alder reactions between C60 and anthracene with high regioselectivity. Catalytic turnover is achieved by the lower stability of the host:guest complex with the resulting C60 cycloadduct, allowing for better conversions in the hydrophobic environment provided by the cage.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Evgenii N. Ivanov, Veronica Almeida-Marrero, Oskar I. Koifman, Viktor V. Aleksandriiskii, Tomas Torres, Mikhail K. Islyaikin
Summary: New substituted [30]trithiadodecaazahexaphyrines (hemihexaphyrazines) were synthesized by a crossover condensation of 2,5-diamino-1,3,4-thiadiazole with 4-chloro-5-(2,6-diisopropylphenoxy)- or 4,5-bis-(2,6-diisopropylphenoxy)phthalonitriles. The compounds were characterized by various spectroscopic and analytical techniques.
Article
Materials Science, Multidisciplinary
Anna-Sophie Wollny, Giulia Lavarda, Ilias Papadopoulos, Ismael Lopez-Duarte, Henrik Gotfredsen, Yuxuan Hou, Rik R. Tykwinski, Tomas Torres, Dirk M. Guldi
Summary: In this study, the energy donor BODIPY is combined with pentacene dimer to form a conjugate BODIPYPnc(2) that can absorb a broad range of solar spectrum. Upon photoexcitation, the singlet excited state energy of BODIPY is transferred to the pentacene dimer through FRET, and then the pentacene dimer undergoes singlet fission. The results indicate that solvent polarity affects the system, with the highest FRET rate and triplet quantum yield obtained in the most polar solvent benzonitrile.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Electrochemistry
Jose Garcia-Calvo, Rosemary R. Cranston, Ismael Lopez-Duarte, Tomas Torres, Benoit H. Lessard
Summary: This article discusses the synthesis and implementation of two novel ruthenium phthalocyanine derivatives in organic thin-film transistors (OTFTs). One derivative showed promising performance, while the other did not. This study provides a promising starting point for the future development of ruthenium phthalocyanine electronic devices.
Article
Pharmacology & Pharmacy
Irene Paramio, Ainhoa Salazar, Mireia Jorda-Redondo, Santi Nonell, Tomas Torres, Gema de la Torre
Summary: In this study, the authors demonstrated the ability of amphiphilic Phthalocyanine (Pc) photosensitizers (PS) to assemble into cationic nanoparticles in water and effectively kill bacterial strains through photoinactivation. The stability and characteristics of the PS nanoparticles were investigated using various spectroscopic and imaging techniques. Among the synthesized PS, PS1 showed the highest efficacy in killing both gram-positive S. aureus and gram-negative E. coli, potentially due to its lower stability and ability to recover the photophysical properties of the non-aggregated species after binding to the bacteria surface.
ADVANCED THERAPEUTICS
(2023)
Article
Materials Science, Multidisciplinary
Jorge Labella, Kazutaka Shoyama, David Guzman, Tim Schembri, Matthias Stolte, Tomas Torres, Frank Wuerthner
Summary: Imide-fused porphyrinoid compounds with naphthalimide were synthesized as NIR-absorbing n-type organic semiconductors. Two different synthetic routes were used, including an annulation reaction between a boronic ester and dibromo-NMI, and a cyclotrimerization of NMI-fused phthalonitrile. The N-alkyl substituted derivative was utilized as a nonfullerene acceptor in organic solar cells, achieving a highest power conversion efficiency of 7.0%.
ACS MATERIALS LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Jorge Labella, Deb Kumar Bhowmick, Anil Kumar, Ron Naaman, Tomas Torres
Summary: High spin polarization (SP) in studies of chiral induced spin selectivity (CISS) is achieved through proper organization of chiral molecules using anchoring groups or complex supramolecular polymers. A new class of spin filters based on bowl-shaped aromatics show high-quality thin-film formation through simple spin-coating and exhibit high spin filtering properties. Devices containing enantiopure tribromo-subphthalocyanines (SubPcs) demonstrate well-ordered chiral structures and achieve high SPs comparable to current complex methodologies, opening up new possibilities for realistic and efficient spintronic devices based on the CISS effect.
Review
Chemistry, Multidisciplinary
Giulia Lavarda, Jorge Labella, M. Victoria Martinez-Diaz, M. Salome Rodriguez-Morgade, Atsuhiro Osuka, Tomas Torres
Summary: The study of subporphyrinoids is a rapidly expanding research area with potential applications in various fields. To fully utilize their functionalities, the development of novel synthesis methods and a deep understanding of their supramolecular organization are crucial. This review summarizes the recent advances in subporphyrinoids, highlighting their versatility and promising applications.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Jan Joseph, Leandro M. O. Lourenco, Joao P. C. Tome, Tomas Torres, Dirk M. Guldi
Summary: Controlling the molecular architecture of organic building blocks and linking their functionalities with solar-light converting systems is a challenge in materials science. In this study, versatile organic molecules were used as building blocks and their charge transfer characteristics were investigated.
