Topochemical Polymerization at Diacetylene Metal-Organic Framework Thin Films for Tuning Nonlinear Optics.

Developing the topochemical polymerization of metal-organic frameworks (MOFs) is of pronounced significance for expanding their functionalities but is still a challenge on third-order nonlinear optics (NLO). Here, we report diacetylene MOF (CAS-1-3) films prepared using a stepwise deposition method and film structural transformation approach, featuring dynamic structural diversity. The MOF structures were determined by the three-dimensional electron diffraction (3D ED) method from nanocrystals collected from the films, which provides a reliable strategy for determining the precise structure of unknown MOF films. We demonstrate the well-aligned diacetylene groups in the MOFs can promote topological polymerization to produce a highly conjugated system under thermal stimulation. As a result, the three MOF films have distinct NLO properties: the CAS-1 film exhibits saturable absorption (SA) while CAS-2 and CAS-3 films exhibit reverse saturable absorption (RSA). Interestingly, due to the topochemical polymerization of the MOF films, a transition from SA to RSA response was observed with increasing temperatures, and the optical limiting effect was significantly enhanced (∼46 times). This study provides a new strategy for preparing NLO materials and thermally regulation of nonlinear optics.

Host-Guest Metal-Organic Frameworks-Based Long-Afterglow Luminescence Materials.

Long-afterglow materials have a broad of applications in optoelectronic devices, sensors, medicine and other fields due to their excellent luminescent properties. The host-guest long-afterglow MOFs material combines the advantages of multi-component characteristics and the stability of MOFs, which improves its luminous performance and expands its other properties. This review introduces the classification, synthesis and application of host-guest MOFs materials with long afterglow. Due to their rigid frames and multi-channel characteristics, MOFs can load common guest materials including rare earth metals, organic dyes, carbon dots, etc. The synthesis methods of loading guest materials into MOFs include solvothermal synthesis, post-encapsulation, post-modification, etc. Those long-afterglow host-guest MOFs have a wide range of applications in the fields of sensors, information security and biological imaging.

Metal-Organic Framework-Based Photodetectors.

The unique and interesting physical and chemical properties of metal-organic framework (MOF) materials have recently attracted extensive attention in a new generation of photoelectric applications. In this review, we summarized and discussed the research progress on MOF-based photodetectors. The methods of preparing MOF-based photodetectors and various types of MOF single crystals and thin film as well as MOF composites are introduced in details. Additionally, the photodetectors applications for X-ray, ultraviolet and infrared light, biological detectors, and circularly polarized light photodetectors are discussed. Furthermore, summaries and challenges are provided for this important research field.

Chiral Liquid Crystalline Metal-Organic Framework Thin Films for Highly Circularly Polarized Luminescence.

Combining metal-organic frameworks (MOFs) with liquid crystals to construct liquid crystalline MOFs (LCMOF) offers the advantage of endowing and enhancing their functionality, yet it remains a challenging task. Herein, we report chiral liquid crystalline MOF (CLCMOF) thin films by cross-linking the chiral liquid crystals (CLC) with MOF thin films to realize highly circular polarization luminescence (CPL) performance with photo and thermal switching. By layer by layer cross-linking stilbene-containing CLC with stilbene-based MOF (CLC/MOF) thin film, the CLCMOF thin films were successfully obtained after UV irradiation due to the abundant [2 + 2] photocycloaddition. The resulted CLCMOF thin films have strong chirality, obvious photochromic fluorescent, and strong CPL performance (the asymmetry factor reaches to 0.4). Furthermore, due to the photochromic fluorescent MOF and thermotropic CLC, the CPL can be reversed and red-shifted after heating and UV irradiation treatment, showing photo- and thermal CPL switching. Such MOF-based CPL thin films with photo/thermal CPL switching were prepared to patterns and codes for the demonstration of potential application in advanced information anticounterfeit and encryption. This study not only opens a strategy for developing chiral thin films combining MOFs and liquid crystals but also offers a new route to achieve CPL switching in optical applications.

Photo-Curable 3D Printing of Circularly Polarized Afterglow Metal-Organic Framework Monoliths.

Developing coordination complexes (such as metal-organic frameworks, MOFs) with circularly polarized luminescence (CPL) is currently attracting tremendous attention and remains a significant challenge in achieving MOF with circularly polarized afterglow. Herein, MOFs-based circularly polarized afterglow is first reported by combining the chiral induction approach and tuning the afterglow times by using the auxiliary ligands regulation strategy. The obtained chiral R/S-ZnIDC, R/S-ZnIDC(bpy), and R/S-ZnIDC(bpe)(IDC = 1H-Imidazole-4,5-dicarboxylate, bpy = 4,4'-Bipyridine, bpe = trans-1,2-Bis(4-pyridyl) ethylene) containing a similar structure unit display different afterglow times with 3, 1, and <0.1 s respectively which attribute to that the longer auxiliary ligand hinders the energy transfer through the hydrogen bonding. The obtained chiral complexes reveal a strong chiral signal, obvious photoluminescence afterglow feature, and strong CPL performance (glum up to 3.7 × 10-2). Furthermore, the photo-curing 3D printing method is first proposed to prepare various chiral MOFs based monoliths from 2D patterns to 3D scaffolds for anti-counterfeiting and information encryption applications. This work not only develops chiral complexes monoliths by photo-curing 3D printing technique but opens a new strategy to achieve tunable CPL afterglow in optical applications.

Electro-Induced Phase Transformation of a Conductive Metal-Organic Framework Film for Nonlinear Optical Switching.

Achieving metal-organic frameworks (MOFs) with nonlinear optical (NLO) switching is profoundly important. Herein, the conductive MOFs Cu-TCNQ phase I (Ph-I) and phase II (Ph-II) films were prepared using the liquid-phase-epitaxial layer-by-layer spin-coating method and steam heating method, respectively. Electronic experiments showed that the Ph-II film could be changed into the Ph-I film under an applied electric field. The third-order NLO results revealed that the Ph-I film had a third-order nonlinear reverse saturation absorption (RSA) response and the Ph-II film displayed a third-order nonlinear saturation absorption (SA) response. With increases in the heating time and applied voltage, the third-order NLO response realized the reversible transition between SA and RSA. The theoretical calculations indicated that Ph-I possessed more interlayer charge transfer, resulting in a third-order nonlinear RSA response that was stronger than that of Ph-II. This work applies phase-transformed MOFs to third-order NLO switching and provides new insights into the nonlinear photoelectric applications of MOFs.

Layer by Layer Spraying Fabrication of Aggregation-Induced Emission Metal-Organic Frameworks Thin Film.

The development of new metal-organic frameworks (MOFs) thin films is important for expanding their functions and applications. Herein, we first report a new kind of MOF thin film by using aggregation-induced emission (AIE) dicarboxyl ligand through a liquid-phase epitaxial (LPE) layer-by-layer (LBL) spraying method (named AIE surface-coordinated metal-organic frameworks thin film, AIE-SURMOF). The obtained AIE-SURMOF Zn4O(TPE)3 (ZnTPE) has highly growth orientation and homogeneous thin film, showing strong fluorescent property. Furthermore, by loading chiral guest in the MOF pore, the formed chiral encapsulated AIE-SURMOF can clearly indicate obvious circularly polarized luminescence performance with glum of 0.01. This study provides new MOF thin film and new strategy for expanding function and application of MOF materials.

In-Situ Formed Electron Inhibitor Enabling Dendrite-free Garnet Electrolytes: A Case Study of Fumed Silica.

Ta-doped Li7La3Zr2O12 (LLZTO) solid-state electrolytes (SEs) show great promise for solid-state batteries due to its high conductivity and safety. However, one of the challenges it faces is lithium dendrite propagation upon long-term cycling. To address this issue, we propose the incorporation of fumed silica (FS) at the grain boundaries of LLZTO to modify the properties of the garnet pellet, which effectively inhibits the dendrite growth. The introduction of FS has demonstrated several beneficial effects. Firstly, it reduces the migration barrier of lithium ions, which helps prevent dendrite formation and propagation. Additionally, FS reduces the electronic conductivity of the SEs pellet, suppressing the dendrite formation. Moreover, the formed lithium silicates from FS might also be acted as electron inhibitor, thus inhibiting the lithium dendrite growth upon cycling. By investigating the use of FS as a modifier in LLZTO-based electrolytes, our study contributes to advancing dendrite-free solid-state electrolytes and thus the development of high-performance all-solid-state batteries.

Maternal supplementation with konjac glucomannan improves maternal microbiota for healthier offspring during lactation.

BACKGROUND: The maternal diet during gestation and lactation affects the health of the offspring. Konjac glucomannan (KGM) is a significantly functional polysaccharide in food research, possessing both antioxidant and prebiotic properties. However, the mechanisms of how KGM regulates maternal nutrition remain insufficient and limited. This study aimed to investigate maternal supplementation with KGM during late gestation and lactation to benefit both maternal and offspring generations. RESULTS: Our findings indicate that KGM improves serum low density lipoprotein cholesterol (LDL-C) and antioxidant capacity. Furthermore, the KGM group displayed a significant increase in the feed intake-related hormones neuropeptide tyrosine (NPY), Ghrelin, and adenosine monophosphate-activated kinase (AMPK) levels. KGM modified the relative abundance of Clostridium, Candidatus Saccharimonas, unclassified Firmicutes, and unclassified Christensenellaceae in sow feces. Acetate, valerate, and isobutyrate were also improved in the feces of sows in the KGM group. These are potential target bacterial genera that may modulate the host's health. Furthermore, Spearman's correlation analysis unveiled significant correlations between the altered bacteria genus and feed intake-related hormones. More importantly, KGM reduced interleukin-6 (IL-6) levels in milk, further improved IL-10 levels, and reduced zonulin levels in the serum of offspring. CONCLUSION: In conclusion, maternal dietary supplementation with KGM during late gestation and lactation improves maternal nutritional status by modifying maternal microbial and increasing lactation feed intake, which benefits the anti-inflammatory capacity of the offspring serum. © 2024 Society of Chemical Industry.

Facile Synthesis of Novel Ti2C Nano Bipyramids for Photothermal and Photodynamic Therapy of Breast Cancer.

Photo-responsive synergetic therapeutics achieved significant attraction in cancer theranostic due to the versatile characteristics of nanomaterials. There have been substantial efforts in developing the simplest nano-design with exceptional synergistic properties and multifunctionalities. In this work, biocompatible Ti2C MXene nano bipyramids (MNBPs) were synthesized by hydrothermal method with dual functionalities of photothermal and photodynamic therapies. The MNBPs shape was obtained from two-dimensional (2D) Ti2C nanosheets by controlling the temperature of the reaction mixture. The structure of these Ti2C MNBPs was characterized by a high-resolution transmission electron microscope, scanning electron microscope, atomic force microscope, X-ray photoelectron spectroscopy, and X-ray diffraction. The Ti2C NBPs have shown exceptional photothermal properties with increased temperature to 72.3 °C under 808 nm laser irradiation. The designed nano bipyramids demonstrated excellent cellular uptake and biocompatibility. The Ti2C NBP has established a remarkable photothermal therapy (PTT) effect against 4T1 breast cancer cells. Moreover, Ti2C NBPs showed a profound response to UV light (6 mW/cm2) and produced reactive oxygen species, making them useful for photodynamic therapy (PDT). These in-vitro studies pave a new path to tune the properties of photo-responsive MXene nanosheets, indicating a potential use in biomedical applications.

Anion-encapsulating, discrete prism and extended frusta, from trimetallated triangular macrocycles and linkers.

Reaction of a trinuclear triangular macrocyclic complex Pb3L(CF3SO3)6 with bidentate linkers in a ratio of 3 equiv. of linker per 2 equiv. of complex, produces a prismatic structure with 4,4'-dipyridyl, and two unprecedented, extended 3D frustum-like structures with 1,2-di(4-pyridyl)ethylene and 1,4-di(4-pyridyl)benzene. The cavities of these structures encapsulate triflate anions.

Inducing Circularly Polarized Luminescence by Confined Synthesis of Ultrasmall Chiral Carbon Nanodot Arrays in Pyrene-Based MOF Thin Film.

Combining the features of the host-guest system and chirality is an efficient strategy to achieve circularly polarized luminescence (CPL). Herein, well-defined chiral carbon nanodot (chirCND) arrays were confined-synthesized by low-temperature calcination of a chiral amino acid loaded metal-organic framework (MOF) to induce high CPL. An achiral porous pyrene-based MOF NU-1000 thin film as the host template was prepared by a liquid-phase epitaxial layer-by-layer fashion, and chiral amino acids as the carbon sources could be confined in the porous MOF and carbonized to homogeneous and ultrasmall chirCND arrays, resulting in a chirCNDs@NU-1000 thin film (l-CNDsx@NU-1000; x = l-cysteine (cys), l-serine, l-histidine, l-glutamic acid, and l-pyroglutamic acid). The results show the pristine chirCNDs by directly carbonizing chiral amino acids hardly endow them with a CPL property. By contrast, benefiting from the arrayed confinement and coordination interaction between chirCNDs and NU-1000, the chirality transfer on the excited state of chirCNDs@NU-1000 is enabled, leading to strong CPL performance (a high luminescence dissymmetry factor glum of l-CNDscys@NU-1000 thin film reached 1.74 × 10-2). This study of chirCNDs encapsulated in fluorescent MOF thin films provides a strategy for developing uniform chiral carbon nanoarrays and offers chiral host-guest thin-film materials for optical applications.

Predict the Polarizability and Order of Magnitude of Second Hyperpolarizability of Molecules by Machine Learning.

In order to determine the polarizability and hyperpolarizability of a molecule, several key parameters need to be known, including the excitation energy of the ground and excited states, the transition dipole moment, and the difference of dipole moment between the ground and excited states. In this study, a machine-learning model was developed and trained to predict the molecular polarizability and second-order hyperpolarizability on a subset of QM9 data set. The density of states was employed as input to the model. The results demonstrated that the machine-learning model effectively estimated both polarizability and the order of magnitude of second-order hyperpolarizability. However, the model was unable to predict the dipole moment and first-order hyperpolarizability, suggesting limitations in its ability to predict the difference of dipole moment between the ground and excited states. The computational efficiency of machine-learning models compared to traditional quantum mechanical calculations enables the possibility of large-scale screening of molecules that satisfy specific requirements using existing databases. This work presents a potential solution for the efficient exploration and analysis of molecules on a larger scale.

Highly Efficient Light Helicity Detection of Enantiomers by Chiral Metal-Organic Framework Thin Films.

The potential of chiral metal-organic frameworks (MOFs) for circularly polarized (CP) optics has been largely unexplored. Herein, we have successfully deposited monolithic and highly oriented chiral MOF thin films prepared by a layer-by-layer method (referred to as surface-coordinated MOF thin films, SURMOF) to fabricate CP photodetection devices and distinguish enantiomers. The helicity-sensitive absorption induced by a pair of enantiopure oriented SURMOF was found to be excellent, with an anisotropy factor reaching 0.41. Moreover, the chiral SURMOFs exhibited a pronounced difference in the uptake of the l- and d-tryptophan enantiomers. To demonstrate the potential of these novel MOF thin films for chirality analysis, we fabricated a portable sensor device that allows for chiral recognition by monitoring the photocurrent signals. Our findings not only introduce a new concept of using chiral building blocks for realizing direct CP photodetectors but also provide a blueprint for novel devices in chiral optics.

Erasable Photopatterning of Stilbene-Based Metal-Organic Framework Films.

The development of photosensitive materials for erasable photopatterning is of significant interest in anti-counterfeiting and information storage applications. Herein two kinds of stilbene-based metal-organic framework (MOF) films with layer by layer method for studying photopatterning is reported. The resulting 2D Zn2 (sdc)2 MOF film (sdc = 4,4'-stilbenedicarboxylate) exhibits excellent photosensitive features with a very short photoconversion time (<35 s) while the 3D MOF Zn4 O(sdc)6 film does not have the property due to the fact that only parallel and short distance arrangement of olefin groups in the adjacent MOF layers can trigger [2+2] photocycloaddition. Furthermore, the Zn2 (sdc)2 film indicates obvious reversible fluorescent photoswitch behavior between yellow and blue fluorescence emission, which can achieve high-efficient, erasable photopatterning with various sizes (ca. 20 microns to decimeter). This study not only develops a new kind of photosensitive crystalline network film but also provides erasable photopatterning from macroscopic to microscopic in optical applications.

Coordination-Induced Symmetry Breaking on Metal-Porphyrinic Framework Thin Films for Enhanced Nonlinear Optical Limiting.

Structural asymmetry affecting the nonlinear optics (NLO) of metal-organic frameworks (MOFs) is very important in fundamentals and applications but is still a challenge. Herein we develop a series of indium-porphyrinic framework (InTCPP) thin films and provide the first study on the coordination-induced symmetry breaking on their third-order NLO. The continuous and oriented InTCPP(H2) thin films were grown on quartz substrates and then postcoordinated with different cations (Fe2+ or Fe3+Cl-) in InTCPP(H2) (named InTCPP(Fe2+) and InTCPP(Fe3+Cl-)). The third-order NLO results reveal the Fe2+ and Fe3+Cl- coordinated InTCPP thin films have substantially enhanced NLO performance. Moreover, InTCPP(Fe3+Cl-) thin films cause symmetry breaking of microstructures, resulting in a 3-fold increase in the nonlinear absorption coefficient (up to 6.35 × 10-6 m/W) compared to InTCPP(Fe2+). This work not only develops a series of nonlinear optical MOF thin films but also provides new insight into symmetry breaking on MOFs for nonlinear optoelectronic applications.

Post-Assembly Modification of Homochiral Titanium-Organic Cages for Recognition and Separation of Molecular Isomers.

A chiral metal-organic cage (MOC) was extended and fixed into a porous framework using a post-assembly modification strategy, which made it easier to study the host-guest chemistry of the solid-state MOC using a single-crystal diffraction technique. Anionic Ti4 L6 (L=embonate) cage can be used as a 4-connecting crystal engineering tecton, and its optical resolution was achieved, thus homochiral ΔΔΔΔ- and ΛΛΛΛ-[Ti4 L6 ] cages were obtained. Accordingly, a pair of homochiral cage-based microporous frameworks (PTC-236(Δ) and PTC-236(Λ)) were easily prepared by a post-assembly reaction. PTC-236 has rich recognition sites provided by the Ti4 L6 moieties, chiral channels and high framework stability, affording a single-crystal-to-single-crystal transformation for guest structure analyses. Thus it was successfully utilized for the recognition and separation of isomeric molecules. This study provides a new approach for the orderly combination of well-defined MOCs into functional porous frameworks.

Ti3C2Tx-Modified PEDOT:PSS Hole-Transport Layer for Inverted Perovskite Solar Cells.

PEDOT: PSS is a commonly used hole-transport layer (HTL) in inverted perovskite solar cells (PSCs) due to its compatibility with low-temperature solution processing. However, it possesses lower conductivity than other conductive polymers and metal oxides, along with surface defects, limiting its photovoltaic performance. In this study, we introduced two-dimensional Ti3C2Tx (MXene) as an additive in the PEDOT:PSS HTL with varying doping concentrations (i.e., 0, 0.03, 0.05, and 0.1 wt.%) to tune the electrical conductivity of PEDOT:PSS and to modify the properties of the perovskite film atop it. We noted that the grain size of the CH3NH3PbI3 (MAPI3) perovskite layer grown over an optimal concentration of MXene (0.03 wt.%)-doped PEDOT:PSS increased from 250 nm to 400 nm, reducing charge recombination due to fewer grain boundaries. Ultraviolet photoelectron spectroscopy (UPS) revealed increased work function (WF) from 4.43 eV to 4.99 eV with 0.03 wt.% MXene doping, making the extraction of holes easier due to a more favorable energy level alignment with the perovskite. Quantum chemical investigations based on density functional theory (DFT) were conducted at the ωB97XD/6-311++G(d,p) level of theory to provide more insight into the stability, bonding nature, and optoelectronic properties of the PEDOT:PSS-MXene system. The theoretical investigations revealed that the doping of PEDOT:PSS with Ti3C2Tx could cause a significant effect on the electronic properties of the HTL, as experimentally demonstrated by an increase in the electrical conductivity. Finally, the inverted PSCs employing 0.03 wt.% MXene-doped PEDOT:PSS showed an average power conversion efficiency (PCE) of 15.1%, up from 12.5% for a reference PSC employing a pristine PEDOT:PSS HTL. The champion device with a 0.03 wt.% MXene-PEDOT:PSS HTL achieved 15.5% PCE.

Electrically regulating nonlinear optical limiting of metal-organic framework film.

Regulating nonlinear optical (NLO) property of metal-organic frameworks (MOFs) is of pronounced significance for their scientific research and practical application, but the regulation through external stimuli is still a challenging task. Here we prepare and electrically control the nonlinear optical regulation of conductive MOFs Cu-HHTP films with [001]- (Cu-HHTP[001]) and [100]-orientations (Cu-HHTP[100]). Z-scan results show that the nonlinear absorption coefficient (ß) of Cu-HHTP[001] film (7.60 × 10-6 m/W) is much higher than that of Cu-HHTP[100] film (0.84 × 10-6 m/W) at 0 V and the ß of Cu-HHTP[001] and Cu-HHTP[100] films gradually increase to 3.84 × 10-5 and 1.71 × 10-6 m/W at 10 V by increasing the applied voltage, respectively. Due to 2D Cu-HHTP having anisotropy of charge transfer in different orientations, the NLO of MOFs film can be dependent on their growth orientations and improved by tuning the electrical field. This study provides more avenues for the regulation and NLO applications of MOFs.

MXenes Thin Films: From Fabrication to Their Applications.

Two-dimensional MXenes possessed exceptional physiochemical properties such as high electrical conductivity (20,000 Scm-1), flexibility, mechanical strength (570 MPa), and hydrophilic surface functionalities that have been widely explored for energy storage, sensing, and catalysis applications. Recently, the fabrication of MXenes thin films has attracted significant attention toward electronic devices and sensor applications. This review summarizes the exciting features of MXene thin film fabrication methods such as vacuum-assisted filtration (VAF), electrodeposition techniques, spin coating, spray coating, dip-coating methods, and other physical/chemical vapor deposition methods. Furthermore, a comparison between different methods available for synthesizing a variety of MXenes films was discussed in detail. This review further summarizes fundamental aspects and advances of MXenes thin films in solar cells, batteries, electromagnetic interference shielding, sensing, etc., to date. Finally, the challenges and opportunities in terms of future research, development, and applications of MXenes-based films are discussed. A comprehensive understanding of these competitive features and challenges shall provide guidelines and inspiration for further growth in MXenes-based functional thin films and contribute to the advances in MXenes technology.