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Electron spin plays a critical role in chemical processes, particularly in reactions involving metal complexes with unpaired electrons. However, more definitive state-to-state experiments are needed to better elucidate the role of electronic spin. Herein, we chose nickel (II) 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin 1 as a catalyst, which allows switching from a low spin to a high spin state of Ni (II) center through an axial pyridine coordination, for electrocatalytic hydrogen evolution reaction (HER). When pyridine is present, we observed β-hydrogenation of porphyrin through electron transfer followed by proton transfer. In contrast, hydrogen evolution mainly occurs via the concerted proton-coupling electron transfer without pyridine coordination. Similar distinct spin-dependent selectivity was also observed in chemical reduction of 1 by CoCp 2 with subsequent addition of pyridinium p-toluenesulfonate. Computational calculations using density functional theory demonstrated that the transition from low spin to high spin state enriches the ligand's electron density after one-electron reduction, leading to preferential protonation of β-periphery rather than meso-position or metal center., (© 2024 Wiley-VCH GmbH.)

Antibiotic resistance has emerged as a global public health crisis in the 21 st century, leading to treatment failures. To address this issue, the medical and pharmaceutical sectors are confronted with two challenges: i) finding potent new antimicrobial agents that would work against resistant-pathogens, and ii) developing conceptually new or unconventional strategies by which a particular antibiotic would remain effective persistently. Photopharmacology with the aid of reversibly controllable light-active antibiotics that we call "photoantibiotics" shows great promise to meet the second challenge, which has inspired many research laboratories worldwide to align their research in inventing or developing such antibiotics. In this review, we have given an overview of the progress made over the last ten years or so towards developing such photoantibiotics. Although making such antibiotics that hold high antimicrobial potency like the native drugs and subsequently maintain a significant activity difference between light-irradiated and non-irradiated states is very challenging, the progress being reported here demonstrates the feasibility of various approaches to engineer photoantibiotics. This review provides a future perspective on the use of such antibiotics in clinical practice with the identification of potential problems and their solutions., (© 2024 Wiley-VCH GmbH.)

Molecules with Möbius topology have drawn increasing attention from scientists in a variety of fields, such as organic chemistry, inorganic chemistry, and material science. However, synthetic difficulties and the lack of functionality impede their fundamental understanding and practical applications. Here, we report the facile synthesis of an aggregation-induced-emission (AIE)-active macrocycle (TPE-ET) and investigate its analogous triply and singly twisted Möbius topologies. Because of the twisted and flexible nature of the tetraphenylethene units, the macrocycle adjusts its conformations so as to accommodate different guest molecules in its crystals. Moreover, theoretical studies including topological and electronic calculations reveal the energetically favorable interconversion process between triply and singly twisted topologies., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two stable core-modified rubyrins bearing one and two dithienylethene (DTE) units (1 and 2) have been synthesized. With one "closed-form" DTE unit, 1 shows aromaticity associated with its conjugated circuit of 26 π-electrons. In contrast, rubyrin 2 containing one "open-form" DTE unit has nonaromatic properties., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin-state switching to isolated molecules at room temperature (light-driven coordination-induced spin-state switching, or LD-CISSS). Whereas bistability and hysteresis in conventional spin-crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD-CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel-porphyrin as the transition-metal complex and 3-phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni-porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72% paramagnetic Ni-porphyrin after irradiation at 365 nm, 32% paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD-CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light-controlled magnetic levitation are conceivable applications., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Aromatic units tethered with an azo (-N=N-) functionality comprise a unique class of compounds, known as molecular photoswitches, exhibiting a reversible transformation between their E- and Z-isomers in response to photo-irradiation. Photoswitches have been explored extensively in the recent past to prepare dynamic self-assembled materials, optoelectronic devices, responsive biomaterials, and more. Most of such materials involve azobenzenes as the molecular photoswitch and to date, SciFinder lists more than 7000 articles and 1000 patents. Subsequently, a great deal of effort has been invested to improve the photo-isomerization efficiency and related mesoscopic properties of azobenzenes. Recently, azoheteroarenes and cyclic azobenzenes, such as arylazopyrazoles, arylazoisoxazoles, arylazopyridines, and diazocines, have emerged as second generation molecular photoswitches beyond conventional azobenzenes. These photoswitches offer distinct photoswitching behavior and responsive properties which make them highly promising candidates for multifaceted applications ranging from photoresponsive materials to photopharmacophores. In this minireview, we introduce the structural refinement and photoresponsive properties of azoheteroarenes and diazocines and summarize the state-of-the-art on utilizing these photoswitches as responsive building blocks in supramolecular assembly, material science and photopharmacology, highlighting their versatile photochemical behavior, enhanced functionality, and latest applications., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Hydrogel-based soft actuators can operate in sensitive environments, bridging the gap of rigid machines interacting with soft matter. However, while stimuli-responsive hydrogels can undergo extreme reversible volume changes of up to ≈90%, water transport in hydrogel actuators is in general limited by their poroelastic behavior. For poly(N-isopropylacrylamide) (PNIPAM) the actuation performance is even further compromised by the formation of a dense skin layer. Here it is shown, that incorporating a bioinspired microtube graphene network into a PNIPAM matrix with a total porosity of only 5.4% dramatically enhances actuation dynamics by up to ≈400% and actuation stress by ≈4000% without sacrificing the mechanical stability, overcoming the water transport limitations. The graphene network provides both untethered light-controlled and electrically powered actuation. It is anticipated that the concept provides a versatile platform for enhancing the functionality of soft matter by combining responsive and 2D materials, paving the way toward designing soft intelligent matter., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

We have recently shown that highly purified lipoteichoic acid (LTA) represents a major immunostimulatory principle of Staphylococcus aureus. In order to test whether this translates to other bacterial species, we extracted and purified LTA from 12 laboratory-grown species. All LTA induced the release of TNF-alpha, IL-1beta, IL-6 and IL-10 in human whole blood. Soluble CD14 (sCD14) inhibited monokine induction by LTA but failed to confer LTA responsiveness for IL-6 and IL-8 release of human umbilical vein endothelial cells (HUVEC). In a competitive LPS-binding protein (LBP) binding assay, the IC(50) of the tested LTA preparations was up to 3,230-fold higher than for LPS. LBP enhanced TNF-alpha release of human peripheral blood mononuclear cells (PBMC) upon LPS but not LTA stimulation. These data demonstrate a differential role for the serum proteins LBP and sCD14 in the recognition of LPS and LTA. Different efficacies of various anti-CD14 antibodies against LPS vs. LTA-induced cytokine release suggest that the recognition sites of CD14 for LPS and LTA are distinct with a partial overlap. While the maximal achievable monokine release in response to LTA was comparable to LPS, all LTA induced significantly less IL-12 and IFN-gamma. IL-12 substitution increased LTA-inducible IFN-gamma release up to 180-fold, suggesting a critical role of poor LTA-inducible IL-12 for IFN-gamma formation. Pretreatment with IFN-gamma rendered galactosamine-sensitized mice sensitive to challenge with LTA. In conclusion, LTA compared to LPS, are weak inducers of IL-12 and subsequent IFN-gamma formation which might explain their lower toxicity in vivo.

The glycosylphosphatidylinositol-anchored receptor CD14 plays a major role in the inflammatory response of monocytes to lipopolysaccharide. Here, we describe that ceramide, a constituent of atherogenic lipoproteins, binds to CD14 and induces clustering of CD14 to co-receptors in rafts. In resting cells, CD14 was associated with CD55, the Fcgamma-receptors CD32 and CD64 and the pentaspan CD47. Ceramide further recruited the complement receptor 3 (CD11b/CD18) and CD36 into proximity of CD14. Lipopolysaccharide, in addition, induced co-clustering with Toll-like receptor 4, Fcgamma-RIIIa (CD16a) and the tetraspanin CD81 while CD47 was dissociated. The different receptor complexes may be linked to ligand-specific cellular responses initiated by CD14.

Tissue macrophages and their precursors-the blood monocytes-respond rapidly to a bacterial infection with the release of inflammatory mediators. These mediators are involved in the recruitment of phagocytic cells, principally neutrophils, from the blood to the site of infection. To initiate this process macrophages and monocytes must be able to detect the presence of bacteria in a reliable, but nevertheless nonspecific, fashion. It is thought that this is achieved by means of receptors on the cell surface which recognize structures common to many different bacteria. One candidate for such a "pattern recognition element" is the cell surface glycoprotein CD14. CD14 has been shown to bind components of the Gram-positive cell wall and it also binds soluble lipopolysaccharide released from Gram-negative bacteria. In both cases the interaction with CD14 leads to an activation of the cell. Here we show that human peripheral blood monocytes can, in addition, bind intact Gram-negative bacteria in the presence of serum and this process involves CD14. When CD14 expression is induced on the myelomonocytic cell line U937 by treatment with vitamin D3 the cells concomittently acquire the capacity to bind bacteria. Furthermore, a non-monocytic cell line which does not bind bacteria acquires the capacity to do so when transfected with either the human or mouse CD14 gene. This binding can be inhibited by blocking the CD14 receptor with anti-CD14 antibody or by blocking the ligand on the bacteria with soluble CD14. Finally we demonstrate binding of sCD14 to Escherichia coli. We conclude that in the presence of serum both membrane-bound and soluble forms of CD14 can bind to Gram-negative bacteria. This suggests that CD14 may play a role in the detection and elimination of intact bacteria in vivo.

The receptor for lipopolysaccharide LPS (CD14) exists in a membrane-associated (mCD14) and a soluble form (sCD14). Previous studies indicate that monocytes produce sCD14 by limited proteolysis of the membrane-bound receptor. In this study we demonstrate that human monocytes also produce sCD14 by a protease-independent mechanism. To investigate the molecular nature of this second pathway we studied sCD14 formation in the monocytic cell line Mono Mac 6 (MM6) and in CD14 transfectants. Both MM6 and the CD14 transfectants constitutively produce sCD14 by a protease-independent mechanism. Structural analysis of sCD14 produced by the CD14 transfectants reconfirmed the presence of the COOH terminus predicted from the cDNA. Since glycosylphosphatidylinositol anchor attachment is associated with the removal of a hydrophobic C-terminal signal peptide, our finding demonstrates that the transfectants secrete sCD14 which escaped this posttranslational modification. Identical results obtained for sCD14 derived from peritoneal dialysis fluid of a patient with kidney dysfunction show the in vivo relevance of this pathway for sCD14 production.

The CD14+/CD16+ cells account for about 10% of all blood monocytes. They are characterized by a low level expression of the CD14 molecule and a high level expression of the CD16 (Fc gamma R III) molecule. Polymerase chain reaction analysis of mRNA prevalence in CD14+/CD16+ cells (compared to the regular CD14++ blood monocytes) demonstrates low levels of CD14 transcripts and high levels of CD16 transcripts, suggestive of a transcriptional control for both of these proteins. Analysis of additional cell surface molecules in three-color immunofluorescence reveals that CD14+/CD16+ cells express the Fc gamma R II in all, and Fc gamma R I and ICAM-1 in some donors. Furthermore, class II antigens are expressed at fourfold higher levels, while both, CD11b and CD33 cell surface proteins, are decreased by a factor of two. Transcript levels were reduced in CD14+/CD16+ cells for all three cell surface molecules. Since these phenotypic markers of the CD14+/CD16+ blood monocytes are reminiscent of tissue macrophages, we performed a comparative analysis with alveolar macrophages (AM). These cells are similar to the CD14+/CD16+ monocytes in that they show low levels of CD14 and strong expression of CD16. Furthermore, similar to the CD14+/CD16+ cells, the AM also exhibit higher levels of class II and lower levels of CD11b and CD33 when compared to the regular CD14++ blood monocytes. In vitro induction of maturation of blood monocytes by 5 day culture of peripheral blood mononuclear cells in 10% human serum will result in decreased CD14 and increased CD16 cell surface expression on the monocyte derived macrophages. At the same time, these cells acquire increased levels of class II and decreased levels of CD11b and CD33. Taken together, these data show that CD14+/CD16+ monocytes, while still in circulation, have acquired features in common with mature tissue macrophages.

Modulating charge transfer (CT) interactions between donor and acceptor molecules may give rise to unique dynamic changes in physicochemical properties, exhibiting great importance in supramolecular chemistry and materials science. In this work, we demonstrate the first instance of reversible photomodulation of donor-acceptor (D-A) CT interaction in the solid state. Pyridinium-based chromophore featuring π-conjugated D-A structures can not only function as a good electron acceptor to undergo photoinduced electron transfer (ET) or engage in intermolecular CT interaction, but also exhibit unique dual emission depending on the excitation wavelengths. The rotatable C-C single bonds within D-A pairs enhance the tunability of molecular structure. Through the synergy of a photoinduced ET and an excited-state conformational change, the intermolecular CT interaction can be switched on and off by alternate light irradiation to enable reversibly modulation of the affinity between donor and acceptor molecules, accompanied by visual color switching and fluorescence on-off as feedback signals., (© 2024 Wiley-VCH GmbH.)

Differently substituted pyrrole-azo-benzene molecular photoswitches were prepared in a straightforward synthetic way. Their fundamental properties were investigated by XRD analysis, differential scanning calorimetry, thermogravimetric analysis, cyclic voltammetry, UV-Vis absorption spectroscopy, Hyper-Rayleigh Scattering, and NMR spectroscopy; the experimental results were further corroborated by DFT calculations. Thermal robustness, the HOMO/LUMO levels, and the absorption properties were altered mostly by substituting the N-methylpyrrole moiety and further fine-tuned by modifying the benzene substituents. The pyrrole substituent also proved crucial for the second-order non-linear optical (NLO) response as well as the photoswitching performance. Both fast and slow molecular switches can be designed with the half-life of the (Z) -isomer ranging from 48 seconds to 23.28 hours and the E/Z molar ratio up to 12/88. This comprehensive study allowed elucidation of the fundamental structure-property relationships and subsequently addresses the key aspects of the property tuning via substitution in molecular azo-photoswitches., (© 2024 Wiley-VCH GmbH.)

Trifluoromethylarenes (ArCF 3 ) are crucial bioisosteres in medicinal chemistry, but catalyst-free and controlled photo-activation of the ArC(sp 3 )-F bond remains a significant challenge. The photo-induced defluorination acyl fluoride exchange (photo-DAFEx) of m-trifluoromethylaniline, induced by ultraviolet light, emerges as a promising novel photo-click reaction for photoaffinity drug discovery. However, the photophysical properties of NMe 2 PhF 2 C(sp 3 )-F derivatives and factors affecting ArC(sp 3 )-F bond activation in photo-DAFEx are not yet fully understood, hindering the development of new photo-defluorination reagents with longer absorption wavelength for the photo-DAFEx. Herein, the photophysical properties, the related mechanism and their affecting factors of a series of ArCF 3 compounds are systematically studied using (TD)DFT methods. The skeleton of aromatic core is found to be intimately related to the absorption wavelength needed for ArC(sp 3 )-F bond activation. A photo-induced intramolecular single-electron activation model was proposed to rationalize the photo-activation of the ArC(sp 3 )-F bond. The transfer of excited electron to C(sp 3 )-F antibonding orbital determined the activation. Based on the above knowledge, three novel ArCF 3 reagents with extended excitation wavelength were designed and predicted, and the absorption spectra and photo-defluorination reactivity of two of them with visible absorption wavelength were validated experimentally, which provided a theoretical guidance for designing next-generation photo-DAFEx., (© 2024 Wiley-VCH GmbH.)

Azo-compounds molecules and phase change materials offer potential applications for sustainable energy systems through the storage and controllable release photochemical and phase change energy. Developing novel and highly efficient Azo-based solar thermal fuels (STFs) for photothermal energy storage and synergistic cooperation with organic phase change materials present significant challenges. Herein, three types of (ortho-, meta-, and para-) azopyridine polymers hinged with flexible alkyl chain are synthesized, in which meta-azopyridine polymer exhibits striking photothermal storage capacity of 430 J/g, providing a feasibility solution for developing high energy density Azo-based STFs. Furthermore, a stable two-phase hybrid system was innovatively constructed by combining the meta-azopyridine polymer with organic phase change materials leveraging hydrogen bonds and van der Waals interactions to collectively harness phase change energy and photothermal energy. The organic phase change material not only supplies additional phase change latent heat but also serves as a solvent, offering abundant free volume for the photo-induced isomerization of the azopyridine chromophores, which successfully circumvents the low charging efficiency in the condensed state and reliance on solvent-assisted charging in traditional Azo-based STFs. This study demonstrates the energy distribution and utilization for household consumers and the photothermal-assisted insulation strategy, achieving more extensive potential implementation for STFs., (© 2024 Wiley-VCH GmbH.)

The development of durable photosensitizers is pivotal for advancing phototherapeutic applications in biomedicine. Here, we introduce a core-shell azobenzene-spiropyran structure on gold nanoparticles, engineered to enhance singlet oxygen generation. These nano-photosensitizers exhibit increased structural stability and thermal resistance, as demonstrated by slowed O-N-C bond recombination dynamics via in-situ Raman spectroscopy. Notably, the in-situ formation of merocyanine and a light-induced compact shell arrangement extend its half-life from 47 minutes to over 154 hours, significantly boosting singlet oxygen output. The nano-photosensitizer also shows high biocompatibility and notably inhibits tau protein aggregation in neural cells, even with phosphatase inhibitors. Further, it promotes dendritic growth in neuro cells, doubling typical lengths. This work not only advances chemical nanotechnology but also sets a foundation for developing long-lasting phototherapy agents for treating neurodegenerative diseases., (© 2024 Wiley-VCH GmbH.)

The incorporation of molecular switches on nanodevices requires both the intactness of the molecule once deposited on a substrate and the persistence of the reversible switching feature. Recently, the reversible spin-switching of strapped Ni(II)-porphyrin complexes deposited on Ag(111) surface is demonstrated with low-temperature scanning tunneling microscopy (STM). The spin transition is accompanied by the coordination change of the metal center, a phenomenon denominated in coordination-induced spin-state switching (CISSS). In this contribution, the spin switching of the deposited strapped Ni-porphyrin molecules using different quantum chemistry approaches is explored. This calculations inform about the geometry and electronic structure of the adsorbed molecules and the origin of the voltage-dependent switching promoted by the STM tip. Two different mechanisms are inspected to elucidate the key role of the tip, mainly the electron injection between the tip and the molecule and the differential stabilization of the two spin states by the applied electric field between the tip and the silver surface. This study puts in evidence the relevance of the pyridine ligand contained in the strap in the transport properties as in the CISSS process itself., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Alzheimer's disease (AD) is a chronic, insidious, and progressive neurodegenerative disease that remains a clinical challenge for society. The fully approved drug lecanemab exhibits the prospect of therapy against the pathological processes, while debatable adverse events conflict with the drug concentration required for the anticipated therapeutic effects. Reactive oxygen species (ROS) are involved in the pathological progression of AD, as has been demonstrated in much research regarding oxidative stress (OS). The contradiction between anticipated dosage and adverse event may be resolved through targeted transport by biomaterials and get therapeutic effects through pathological progression via regulation of ROS. Besides, biomaterials fix delivery issues by promoting the penetration of drugs across the blood-brain barrier (BBB), protecting the drug from peripheral degradation, and elevating bioavailability. The goal is to comprehensively understand the mechanisms of ROS in the progression of AD disease and the potential of ROS-related biomaterials in the treatment of AD. This review focuses on OS and its connection with AD and novel biomaterials in recent years against AD via OS to inspire novel biomaterial development. Revisiting these biomaterials and mechanisms associated with OS in AD via thorough investigations presents a considerable potential and bright future for improving effective interventions for AD., (© 2024 Wiley‐VCH GmbH.)

A problem of systemic pharmacotherapy is off-target activity, which causes adverse effects. Outstanding examples include neuroinhibitory medications like antiseizure drugs, which are used against epilepsy and neuropathic pain but cause systemic side effects. There is a need of drugs that inhibit nerve signals locally and on-demand without affecting other regions of the body. Photopharmacology aims to address this problem with light-activated drugs and localized illumination in the target organ. Here, we have developed photoswitchable derivatives of the widely prescribed antiseizure drug carbamazepine. For that purpose, we expanded our method of ortho azologization of tricyclic drugs to meta/para and to N-bridged diazocine. Our results validate the concept of ortho cryptoazologs (uniquely exemplified by Carbazopine-1) and bring to light Carbadiazocine (8), which can be photoswitched between 400-590 nm light (using violet LEDs and halogen lamps) and shows good drug-likeness and predicted safety. Both compounds display photoswitchable activity in vitro and in translucent zebrafish larvae. Carbadiazocine (8) also offers in vivo analgesic efficacy (mechanical and thermal stimuli) in a rat model of neuropathic pain and a simple and compelling treatment demonstration with non-invasive illumination., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Visuomorphic computing aims to simulate and potentially surpass the human retina by mimicking biological visual perception with an artificial retina. Despite significant progress, challenges persist in perceiving complex interactive environments. Negative photoconductivity transistors (NPTs) mimic synaptic behavior by achieving adjustable positive photoconductivity (PPC) and negative photoconductivity (NPC), simulating "excitation" and "inhibition" akin to sensory cell signals. In complex interactive environments, NPTs are desired for visuomorphic computing that can achieve a better sense of information, lower power consumption, and reduce hardware complexity. In this review, it is started by introducing the development process of NPTs, while placing a strong emphasis on the device structures, working mechanisms, and key performance parameters. The common material systems employed in NPTs based on their functions are then summarized. Moreover, it is proceeded to summarize the noteworthy applications of NPTs in optoelectronic devices, including advanced multibit nonvolatile memory, optoelectronic logic gates, optical encryption, and visual perception. Finally, the challenges and prospects that lie ahead in the ongoing development of NPTs are addressed, offering valuable insights into their applications in optoelectronics and a comprehensive understanding of their significance., (© 2024 Wiley‐VCH GmbH.)

Due to the broadband response and low selectivity of external light, negative photoconductivity (NPC) effect holds great potential applications in photoelectric devices. Herein, different photoresponsive carbon nanodots (CDs) are prepared from diverse precursors and the broadband response from the NPC CDs are utilized to achieve the optoelectronic logic gates and optical imaging for the first time. In detail, the mcu-CDs which are prepared by the microwave-assisted polymerization of citric acid and urea possess the large specific surface area and abundant hydrophilic groups as sites for the adsorption of H 2 O molecules and thereby present a high conductivity in dark. Meanwhile, the low affinity of mcu-CDs to H 2 O molecules permits the light-induced desorption of H 2 O molecules by heat effect and thus endow the mcu-CDs with a low conductivity under illumination. The easy absorption and desorption of H 2 O molecules contribute to the extraordinary NPC of mcu-CDs. With the broadband NPC response in CDs, the optoelectronic logic gates and flexible optical imaging system are established, achieving the applications of "NOR" or "NAND" logic operations and high-quality optical images. These findings unveil the unique optoelectronic properties of CDs, and have the potential to advance the applications of CDs in optoelectronic devices., (© 2024 Wiley‐VCH GmbH.)

19 F magnetic resonance (MR) based detection coupled with well-designed inorganic systems shows promise in biological investigations. Two proof-of-concept inorganic probes that exploit a novel mechanism for 19 F MR sensing based on converting from low-spin (S=0) to high-spin (S=1) Ni 2+ are reported. Activation of diamagnetic NiL 1 and NiL 2 by light or β-galactosidase, respectively, converts them into paramagnetic NiL 0 , which displays a single 19 F NMR peak shifted by >35 ppm with accelerated relaxation rates. This spin-state switch is effective for sensing light or enzyme expression in live cells using 19 F MR spectroscopy and imaging that differentiate signals based on chemical shift and relaxation times. This general inorganic scaffold has potential for developing agents that can sense analytes ranging from ions to enzymes, opening up diverse possibilities for 19 F MR based biosensing., (© 2020 Wiley-VCH GmbH.)

Integrating controllable spin states into single-molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d-4f metallacrown (MC) magnet [DyNi 5 (quinha) 5 ( Cl sal) 2 (py) 8 ](ClO 4 ) ⋅ 4H 2 O (H 2 quinha=quinaldichydroxamic acid, H Cl sal=5-chlorosalicylaldehyde) wherein a square planar Ni II is stabilized by chemical stacking. Thioacetal modification was employed via post-synthetic ligand substitutions and yielded [DyNi 5 (quinha) 5 ( Cl saldt) 2 (py) 8 ](ClO 4 ) ⋅ 3H 2 O (H Cl saldt=4-chloro-2-(1,3-dithiolan-2-yl)phenol). Thanks to the additional ligations of thioacetal onto the Ni II site, coordination-induced spin state switching (CISSS) took place with spin state altering from low-spin S=0 to high-spin S=1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57 cm -1 to 423 cm -1 , along with hysteresis opening and an over 200-fold increment in coercive field at 2 K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire-new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach., (© 2024 Wiley-VCH GmbH.)

Metal-organic frameworks (MOFs), renowned for their exceptional porosity and crystalline structure, stand at the forefront of gas adsorption and separation applications. Shortly after their discovery through experimental synthesis, computational simulations quickly become an important method in broadening the use of MOFs by offering deep insights into their structural, functional, and performance properties. This review specifically addresses the pivotal role of molecular simulations in enlarging the molecular understanding of MOFs and enhancing their applications, particularly for gas adsorption. After reviewing the historical development and implementation of molecular simulation methods in the field of MOFs, high-throughput computational screening (HTCS) studies used to unlock the potential of MOFs in CO 2 capture, CH 4 storage, H 2 storage, and water harvesting are visited and recent advancements in these adsorption applications are highlighted. The transformative impact of integrating artificial intelligence with HTCS on the prediction of MOFs' performance and directing the experimental efforts on promising materials is addressed. An outlook on current opportunities and challenges in the field to accelerate the adsorption applications of MOFs is finally provided., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Molecular switches, especially azobenzenes, are used in numerous applications, such as molecular solar thermal storage (MOST) systems and photopharmacology. The Baeyer-Mills reaction of anilines and nitrosobenzenes has been established as an efficient synthetic method for non-symmetric azobenzenes. However, nitrosobenzenes are not stable, depending on their substitution pattern and pose a health risk. An in-situ oxidation of anilines with Oxone® was optimized under continuous flow conditions avoiding isolation and contact. The in-situ generated nitrosobenzene derivatives were subjected to a telescoped Baeyer-Mills reaction in flow. That way azobenzenes with a broad substituent spectrum were made accessible., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Three visible-light responsive photoswitches are reported, azobis(1-methyl-benzimidazole) (1), azobis(benzoxazole) (2) and azobis(benzothiazole) (3). Photostationary distributions are obtained upon irradiation with visible light comprising approximately 80 % of the thermally unstable isomer, with thermal half-lives up to 8 min and are mostly invariant to solvent. On protonation, compound 1H + has absorption extending beyond 600 nm, allowing switching with yellow light, and a thermal half-life just under 5 minutes. The two isomers have significantly different pK a values, offering potential as a pH switch. The absorption spectra of 2 and 3 are insensitive to acid, although changes in the thermal half-life of 3 indicate more basic intermediates that significantly influence the thermal barrier to isomerization. These findings are supported by high-level ab initio calculations, which validate that protonation occurs on the ring nitrogen and that the Z isomer is more basic in all cases., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Oxidation of 5,15-dithiaporphyrin with meta-chloroperbenzoic acid afforded the corresponding S,S-tetraoxide in good yield. The resultant 5,5,15,15-tetraoxo-5,15-dithiaporphyrin exhibited the highly electron-deficient nature as elucidated by the electrochemical analysis and theoretical calculations. Treatment of tetraoxodithiaporphyrin with zinc(II) acetate and nickel(II) acetate provided the corresponding metal complexes efficiently. Owing to its enhanced Lewis acidity of the metal center by the electron-deficient ligand, the nickel complex underwent facile axial ligation to form pentacoordinate and hexacoordinate high-spin (S=1) complexes in solution and solid, respectively. The binding constant of pyridine to the Ni II center was significantly higher than those of conventional porphyrin Ni II complexes. Temperature-dependent magnetic susceptibility measurements of the high-spin Ni II complex revealed the presence of weak ferromagnetic interactions., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photoswitches are molecules that can absorb light of specific wavelengths and undergo a reversible transformation between their trans and cis isomeric forms. In phenylazo photoswitches, it is common for the less stable cis (Z) isomer to convert back to the more stable trans (E) isomer either through photochemical or thermal means. In this research, we designed new derivatives of phenylazothiazole (PAT) photoswitches, PAT-F n , which feature fluorine substituents on their phenyl component. These derivatives can reversibly isomerize under visible light exposure with the enrichment of E and Z isomers at photostationary state (PSS). Surprisingly, we observed an unconventional phenomenon when these PAT-F n (n≧2) photoswitches were in their cis isomeric state in the absence of light. Instead of the anticipated transformation from cis to trans isomer, these compounds converted to an oligomeric compound. Our detailed experimental investigation and theoretical calculations, indicated the crucial role of fluorine substituents and the distinctive geometric arrangement of the cis isomer in driving the unexpected oligomerization process originating from the cis isomeric state., (© 2024 Wiley‐VCH GmbH.)

The positive photoconductive (PPC) effect is a well-established primary detection mechanism employed by photodetectors. In contrast, the negative photoconductive (NPC) effect is not extensively investigated thus far, and research on the NPC effect is still in its early stage. Herein, a quaternary van der Waals material, AgBiP 2 Se 6 atomic layers, is discovered to achieve a giant NPC effect. Through experimental observations in a Graphene/AgBiP 2 Se 6 / Graphene-based vertical photodetector, an irreversible conversion is identified from common PPC photoresponse to atypical NPC photoresponse. Notably, this device demonstrates an exceptionally high negative responsivity (R) of 4.9 × 10 5  A W -1 , surpassing the previous records for NPC photodetectors. Additionally, it exhibits remarkable optoelectronic performances, including an external quantum efficiency of 1.3 × 10 8 % and a detectivity (D) of 3.60 × 10 12  Jones. The exceptionally high NPC photoresponse observed in this device can be attributed to the swift suppression of photogenerated free carriers at robust recombination centers situated at significant depths, induced by the elevated drain-source voltage bias. The remarkably high NPC photoresponse also positions AgBiP 2 Se 6 as a promising 2D material for multifunctional optoelectronic devices and an excellent platform for systematic exploration of the NPC effect., (© 2024 Wiley‐VCH GmbH.)

In addition to the discovery of new (modified) potent antibiotics to combat antibiotic resistance, there is a critical need to develop novel strategies that would restrict their off-target effects and unnecessary exposure to bacteria in our body and environment. We report a set of new photoswitchable arylazopyrazole-modified norfloxacin antibiotics that present a high degree of bidirectional photoisomerization, impressive fatigue resistance and reasonably high cis half-lives. The irradiated isomers of most compounds were found to exhibit nearly equal or higher antibacterial activity than norfloxacin against Gram-positive bacteria. Notably, against norfloxacin-resistant S. aureus bacteria, the visible-light-responsive p-SMe-substituted derivative showed remarkably high antimicrobial potency (MIC of 0.25 μg/mL) in the irradiated state, while the potency was reduced by 24-fold in case of its non-irradiated state. The activity was estimated to be retained for more than 7 hours. This is the first report to demonstrate direct photochemical control of the growth of antibiotic-resistant bacteria and to show the highest activity difference between irradiated and non-irradiated states of a photoswitchable antibiotic. Additionally, both isomers were found to be non-harmful to human cells. Molecular modellings were performed to identify the underlying reason behind the high-affinity binding of the irradiated isomer to topoisomerase IV enzyme., (© 2024 Wiley-VCH GmbH.)

Effective wound healing is critical for patient care, and the development of novel wound dressing materials that promote healing, prevent infection, and are user-friendly is of great importance, particularly in the context of point-of-care testing (POCT). This study reports the synthesis of a hydrogel material that can be produced in less than 10 s and possesses antibacterial activity against both gram-negative and gram-positive microorganisms, as well as the ability to inhibit the growth of eukaryotic cells, such as yeast. The hydrogel is formed wholly based on covalent-like hydrogen bonding interactions and exhibits excellent mechanical properties, with the ability to stretch up to more than 600% of its initial length. Furthermore, the hydrogel demonstrates ultra-fast self-healing properties, with fractures capable of being repaired within 10 s. This hydrogel can promote skin wound healing, with the added advantage of functioning as a strain sensor that generates an electrical signal in response to physical deformation. The strain sensor composed of a rubber shell realizes fast and responsive strain sensing. The findings suggest that this hydrogel has promising applications in the field of POCT for wound care, providing a new avenue for improved patient outcomes., (© 2023 Wiley-VCH GmbH.)

Emerging applications of photochromic compounds demand new molecular designs that can be inspired by some long-known yet currently forgotten classes of photoswitches. In the present review, we remind the community about Peri-AryloxyQuinones (PAQs) and their unique photoswitching behavior originally discovered more than 50 years ago. At the heart of this phenomenon is the light-induced migration of an aromatic moiety (arylotropy) in peri-aryloxy-substituted quinones resulting in ana-quinones. PAQs feature absorbance of both isomers in the visible spectral region, photochromism in the amorphous and crystalline state, and thermal stability of the photogenerated ana-isomer. Particularly noticeable is the high sensitivity of the ana-isomer towards nucleophiles in solution. In addition to the mechanism of molecular photochromism and the underlaying structure-switch relationships, we analyze potential applications and prospects of aryloxyquinones in optically switchable materials and devices. Due to their ability to efficiently photoswitch in the solid state, PAQs are indeed attractive candidates for such materials and devices, including electronics (optically controllable circuits, switches, transistors, memories, and displays), porous crystalline materials, crystalline actuators, photoactivated sensors, and many more. This review is intended to serve as a guide for researchers who wish to use photoswitchable PAQs in the development of new photocontrollable materials, devices, and processes., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Polymorphic forms of organic conjugated small molecules, with their unique molecular shapes, packing arrangements, and interaction patterns, provide an excellent opportunity to uncover how their microstructures influence their observable properties. Ethyl-2-(1-benzothiophene-2-yl)quinoline-4-carboxylate (BZQ) exists as dimorphs with distinct crystal habits - blocks (BZB) and needles (BZN). The crystal forms differ in their molecular arrangements - BZB has a slip-stacked column-like structure in contrast to a zig-zag crystal packing with limited π-overlap in BZN. The BZB crystals characterized by extended π-stacking along [100] demonstrated semiconductor behavior, whereas the BZN, with its zig-zag crystal packing and limited stacking characteristics, was reckoned as an insulator. Monotropically related crystal forms also differ in their nanomechanical properties, with BZB crystals being considerably softer than BZN crystals. This discrepancy in mechanical behavior can be attributed to the distinct molecular arrangements adopted by each crystal form, resulting in unique mechanisms to relieve the strain generated during nanoindentation experiments. Waveguiding experiments on the acicular crystals of BZN revealed the passive waveguiding properties. Excitation of these crystals using a 532 nm laser confirmed the propagation of elastically scattered photons (green) and the subsequent generation of inelastically scattered (orange) photons by the crystals. Further, the dimorphs display dissimilar photoluminescence properties; they are both blue-emissive, but BZN displays twice the quantum yield of BZB. The study underscores the integral role of polymorphism in modulating the mechanical, photophysical, and conducting properties of functional molecular materials. Importantly, our findings reveal the existence of light-emitting crystal polymorphs with varying electric conductivity, a relatively scarce phenomenon in the literature., (© 2023 Wiley-VCH GmbH.)

The utilisation of light to achieve precise manipulation and control over the structure and function of supramolecular assemblies has emerged as a highly promising approach in the development of complex, configurable, or multifunctional systems and nanoscopic machine-like entities. In this minireview, we highlight recent examples of self-assembled and covalently bound cages and macrocycles with a focus on the external and internal functionalisation of a structure with a photoswitchable unit or the embedment of a photoswitch into the framework of a structure. Functionalising the interior or exterior of a supramolecular cage or macrocycle with a photoresponsive group enables control over different properties, such as guest binding or assembly in the solid-state, while the overall shape of the assembly often undergoes no significant change. By directly integrating a photoswitchable unit into the framework of a supramolecular structure, the isomerisation can either induce a geometry change, the disassembly, or the disassembly and reassembly of the structure. Historical and recent examples covered in this review are based on azobenzene, diarylethene, stilbene photoswitches, or alkene motors that were incorporated into macrocycles and cages constructed by metal-organic, dynamic covalent, or covalent bonds., (© 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [(2-κ 2 P,κ 6 C)Mo(CO) 2 ][OTf] (3 a[OTf]), [(2-κ 2 P,κ 6 C)Fe(CO)][OTf] (3 b[OTf]), and [(2-κ 2 P)Fe(CO) 4 ][OTf] (4[OTf]) were prepared using the triflate salt [(L C )P=P(Dipp)][OTf] (2[OTf) as a precursor (L C =4,5-dichloro-1,3-bis(2,6-diisiopropylphenyl)-imidazolin-2-yl; Dipp=2,6-diisiopropylphenyl, OTf=triflate). Upon exposure to blue or UV light (λ=400 nm, 470 nm), the initially red-colored η 2 -diphosphene complexes 3 a,b[OTf] readily undergo isomerization to form blue-colored η 1 -complexes [(2-κ 1 P,κ 6 C)M(CO) n ][OTf] (5 a,b[OTf]; a: M=Mo, n=2; b: M=Fe, n=1). This haptotropic rearrangement is reversible, and the (κ 2 P,κ 6 C)-coordination mode gradually reverts back upon dissolution in coordinating solvents or more rapidly upon exposure to yellow or red irradiation (λ=590 nm, 630 nm). The electronic reasons for the reversible visible-light-induced photoswitching observed for 3 a,b[OTf] are elucidated by DFT calculations. These calculations indicate that the photochromic isomerization originates from the S 1 excited state and proceeds through a conical intersection., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Indigo, one of the most ancient and abundant dyes in human history, has recently emerged as a potential functional motif due to its intriguing photochemical properties. This review aims to provide insights into both the preparation of these molecules and their utilization in molecular systems. First, the synthesis of the indigo core as well as available methods to derivatize indigo are described to outline synthetic strategies to build the desired molecular structures. Then, the photochemical behavior of indigos is discussed, with particular focus on E-Z photoisomerization and photoinduced electron transfer. Connections between the molecular structures and their photochemical properties are highlighted and serve as guiding principles for designing indigos to be applied as photoresponsive tools., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Machine learning (ML) algorithms are currently emerging as powerful tools in all areas of science. Conventionally, ML is understood as a fundamentally data-driven endeavour. Unfortunately, large well-curated databases are sparse in chemistry. In this contribution, I therefore review science-driven ML approaches which do not rely on "big data", focusing on the atomistic modelling of materials and molecules. In this context, the term science-driven refers to approaches that begin with a scientific question and then ask what training data and model design choices are appropriate. As key features of science-driven ML, the automated and purpose-driven collection of data and the use of chemical and physical priors to achieve high data-efficiency are discussed. Furthermore, the importance of appropriate model evaluation and error estimation is emphasized., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Azo compounds are efficient electron acceptors. Upon one-electron reduction they generally isomerize forming the thermodynamically most stable radical anion. Herein we show that the size of the central ring in 1,2-diazocines and diazonines has a ruling influence on the configuration of the one-electron reduced species. Markedly, diazonines, which bear a central nine membered heterocycle, show light-induced E/Z isomerization, but retain the configuration of the diazene N=N moiety upon one-electron reduction. Accordingly, E/Z isomerization is not induced by reduction., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Bioelectrodes have been developed to efficiently mediate electrical signals of biological systems as stimulators and recording devices. Recently, conductive hydrogels have garnered great attention as emerging materials for bioelectrode applications because they can permit intimate/conformal contact with living tissues and tissue-like softness. However, administration and control over the in vivo lifetime of bioelectrodes remain challenges. Here, injectable conductive hydrogels (ICHs) with tunable degradability as implantable bioelectrodes are developed. ICHs were constructed via thiol-ene reactions using poly(ethylene glycol)-tetrathiol and thiol-functionalized reduced graphene oxide with either hydrolyzable poly(ethylene glycol)-diacrylate or stable poly(ethylene glycol)-dimaleimide, the resultant hydrogels of which are degradable and nondegradable, respectively. The ICH electrodes had conductivities of 21-22 mS cm -1 and Young's moduli of 15-17 kPa, and showed excellent cell and tissue compatibility. The hydrolyzable conductive hydrogels disappeared 3 days after in vivo administration, while the stable conductive hydrogels maintained their shapes for up to 7 days. Our proof-of-concept studies reveal that electromyography signals with significantly improved sensitivity from rats could be obtained from the injected ICH electrodes compared to skin electrodes and injected nonconductive hydrogel electrodes. The ICHs, offering convenience in use, controllable degradation and excellent signal transmission, will have great potential to develop various bioelectronics devices., (© 2023 Wiley-VCH GmbH.)

Flexible electronics is an emerging field of research involving multiple disciplines, which include but not limited to physics, chemistry, materials science, electronic engineering, and biology. However, the broad applications of flexible electronics are still restricted due to several limitations, including high Young's modulus, poor biocompatibility, and poor responsiveness. Innovative materials aiming for overcoming these drawbacks and boost its practical application is highly desirable. Hydrogel is a class of 3D crosslinked hydrated polymer networks, and its exceptional material properties render it as a promising candidate for the next generation of flexible electronics. Here, the latest methods of synthesizing advanced functional hydrogels and the state-of-art applications of hydrogel-based flexible electronics in various fields are reviewed. More importantly, the correlation between properties of the hydrogel and device performance is discussed here, to have better understanding of the development of flexible electronics by using environmentally responsive hydrogels. Last, perspectives on the current challenges and future directions in the development of hydrogel-based multifunctional flexible electronics are provided., (© 2023 Wiley-VCH GmbH.)

Photoresponsive supramolecular polymers are well-organized assemblies based on highly oriented and reversible noncovalent interactions containing photosensitive molecules as (co-)monomers. They have attracted increasing interest in smart materials and dynamic systems with precisely controllable functions, such as light-driven soft actuators, photoresponsive fluorescent anticounterfeiting and light-triggered electronic devices. The present review discusses light-activated molecules used in photoresponsive supramolecular polymers with their main photo-induced changes, e.g., geometry, dipole moment, and chirality. Based on these distinct changes, supramolecular polymers formed by light-activated molecules exhibit photoresponsive disassembly and reassembly. As a consequence, photo-induced supramolecular polymerization, "depolymerization," and regulation of the lengths and topologies are observed. Moreover, the light-controlled functions of supramolecular polymers, such as actuation, emission, and chirality transfer along length scales, are highlighted. Furthermore, a perspective on challenges and future opportunities is presented. Besides the challenge of moving from harmful UV light to visible/near IR light avoiding fatigue, and enabling biomedical applications, future opportunities include light-controlled supramolecular actuators with helical motion, light-modulated information transmission, optically recyclable materials, and multi-stimuli-responsive supramolecular systems., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

A crucial component in designing soft actuating structures with controllable shape changes is programming internal, mismatching stresses. In this work, a new paradigm for achieving anisotropic dynamics between isotropic end-states-yielding a non-reciprocal shrinking/swelling response over a full actuation cycle-in a microscale actuator made of a single material, purely through microscale design is demonstrated. Anisotropic dynamics is achieved by incorporating micro-sized pores into certain segments of the structures; by arranging porous and non-porous segments (specifically, struts) into a 2D hexagonally-shaped microscopic poly(N-isopropyl acrylamide) hydrogel particle, the rate of isotropic shrinking/swelling in the structure is locally modulated, generating global anisotropic, non-reciprocal, dynamics. A simple mathematical model is introduced that reveals the physics that underlies these dynamics. This design has the potential to be used as a foundational tool for inducing non-reciprocal actuation cycles with a single material structure, and enables new possibilities in producing customized soft actuators and modular anisotropic metamaterials for a range of real-world applications, such as artificial cilia., (© 2022 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.)

Molecular switches have been used as delivery vehicles for various molecular and ionic species. The ones that reversibly operate with light are arguably the best candidates for the purpose as they can be operated using light. The two states of these photoswitchable systems often possess remarkable differences in terms of their structural features and electronic properties. Photochromic systems with the appropriate embellishment of functionalities at suitable positions have thus been used as photoresponsive receptors. The use of light-driven alterations of the structural features has led to differential molecular recognition with these switchable host molecules. In this article, we discuss the use of such supramolecular systems as the delivery vehicles for ions and molecules that started with the pioneering work by Shinkai back in 1979. This review will explicitly cover the development from 2001 to 2022 with some past background and the future prospects of the field., (© 2022 Wiley-VCH GmbH.)

The effective use of photochromic systems based on azo compounds in a number of applications, especially biomedical and pharmacological ones, is impeded by the unresolved problem of their E⇆Z isomerization in the near-IR region, NIR (780-1400 nm). We have demonstrated at the TD-DFT, STEOM-DLPNO-CCSD and CASSCF-NEVPT2 levels of theory that the presence of a silylated diazene core -Si-N=N-Si- with three-, tetra- or five-coordinated silicon atoms practically guarantees the absorption of the E and Z forms of such derivatives in NIR and the amazing (185-400 nm) separation of their first absorption bands. In particular, the maximum λ 1 of the first n→π* band of the E isomer of azosilabenzene ASiB is at ∼1030 nm, while for the Z isomer λ 1 ≅1340 nm. Based on the found bistable azo compounds (ASiB, bis(silyl)- SiD and bis(silatranyl)- SaD diazenes) and their derivatives with E and Z absorption in NIR, unique photoswitches can be created for a number of applications, in particular, for photothermal therapy., (© 2022 Wiley-VCH GmbH.)

Tetra-ortho-substituted, heteroaryl and cyclic azobenzenes have emerged as three key strategies on morphology design of photoswitch to diversify controllability. Cyclic azobenzene is of particular utilization in photo-energy conversion due to rigid and ring-strain structure. Despite the well-recognized diazocine, the photo-switching properties of seven-membered cyclic azobenzenes (diazepines) have yet been exploited. Herein, we report a family of dibenzo[b,f][1,4,5]chalcogenadiazepines (DBChDs) and their T-type photo-switching nature with tunable relaxation rate. Based on experiments together with DFT calculations, we found that an unsymmetric 2-bithiophenyl-dibenzo[b,f][1,4,5]thiadiazepine exhibited an efficient response to 445 nm laser stimulation (quantum efficiency, Φ Z→E =0.71) with millisecond relaxation half-life (t 1/2 =40 ms). Photo-energy transduction efficiency was also exceptionally high with 29.1 % converted into ring-strain energy mainly loaded on azo π-bond., (© 2022 Wiley-VCH GmbH.)

Light offers unique opportunities for controlling the activity of materials and biosystems with high spatiotemporal resolution. Molecular photoswitches are chromophores that undergo reversible isomerization between different states upon irradiation with light, allowing a convenient means to control their influence over the system of interest. However, a significant limitation of classical photoswitches is the requirement to initiate the switching in one or both directions using deleterious UV light with poor tissue penetration. Red-shifted photoswitches are hence in high demand and have attracted keen recent research interest. In this Review, we highlight recent progress towards the development of visible- and NIR-activated photoswitches characterized by distinct photochromic reaction mechanisms. We hope to inspire further endeavors in this field, allowing the full potential of these tools in biotechnology and materials chemistry applications to be realized., (© 2022 Wiley-VCH GmbH.)

Covalent organic frameworks (COFs), an emerging class of organic crystalline polymers with highly oriented structures and permanent porosity, can adopt 2D or 3D architectures depending on the different topological diagrams of the monomers. Notably, 2D COFs have particularly gained much attention due to the extraordinary merits of their extended in-plane π-conjugation and topologically ordered columnar π-arrays. These properties together with high crystallinity, large surface area, and tunable porosity distinguish 2D COFs as an ideal candidate for the fabrication of functional materials. Herein, this review surveys the recent research advances in 2D COFs with special emphasis on the preparation of 2D COF powders, single crystals, and thin films, as well as their advanced optical, electrical, and magnetic functionalities. Some challenging issues and potential research outlook for 2D COFs are also provided for promoting their development in terms of structure, synthesis, and functionalities., (© 2022 Wiley-VCH GmbH.)

Azobenzenes are classical molecular photoswitches that have been widely used. In recent endeavors of molecular design, replacing one or both phenyl rings with heteroaromatic rings has emerged as a strategy to expand molecular diversity and access improved photoswitching properties. Many mono-heteroaryl azo molecules with unique structures and/or properties have been developed, but the potential of bis-heteroaryl architectures is far from fully exploited. We report a family of azobispyrazoles, which combine (near-)quantitative bidirectional photoconversion and widely tunable Z-isomer thermal half-lives from hours to years. The two five-membered rings remarkably weaken the intramolecular steric hindrance, providing new possibilities for engineering the geometric and electronic structure of azo photoswitches. Azobispyrazoles generally exhibit twisted Z-isomers that facilitate complete Z→E photoisomerization, and their thermal stability can be broadly adjusted regardless of the twisted shape, overcoming the conflict between photoconversion (favored by the twisted shape) and Z-isomer stability (favored by the orthogonal shape) encountered by mono-heteroaryl azo switches., (© 2021 Wiley-VCH GmbH.)