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.

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.

Optimizing Photodetectors in Two-Dimensional Metal-Metalloporphyrinic Framework Thin Films.

Two-dimensional (2D) metalloporphyrin-based MOF thin films possessing abundant π-π interactions are promising materials for photoelectronic devices, but no reports on fabrication of photodetectors are available so far. Herein, a series of 2D MOF Zn2[TCPP(M)] (named ZnTCPP(M); TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin; M = Zn, Mn, Fe, and H2) films with [001] orientation are fabricated on SiO2/Si substrates by the liquid-phase epitaxial (LPE) layer-by-layer (lbl) approach and further assembled to photodetectors. The obtained ZnTCPP(M)-based photodetectors exhibit an excellent photoresponse due to abundant π-π stacking between the MOF layers. Moreover, the metalloporphyrinic groups in ZnTCPP(M) have a significant influence on modulating the photoresponse of the photodetectors, among which the prepared ZnTCPP(Zn) film-based device exhibits the best photodetection performance with a high on/off ratio of 2.3 × 104, responsivity (Rλ, up to 10.3 A W-1), short rise/fall times (0.09/0.07 s), and a large detectivity (D*) of 8.1 × 1013 Jones. Density functional theory (DFT) calculations reveal that the perturbation of the ring π-electron system and the introduction of low-lying states as well as the large delocalization of the metalloporphyrinic group will adjust the photodetection performance of ZnTCPP(M) films. These results will provide a new understanding of the modulation of 2D metalloporphyrinic MOFs toward photodetection performance and perspective for the fabrication of photoelectronic devices.

Chiral-Induced Ultrathin Covalent Organic Frameworks Nanosheets with Tunable Circularly Polarized Luminescence.

Development of covalent organic frameworks (COFs) with circularly polarized luminescence (CPL) is still challenging. Here we first reported ultrathin COFs nanosheets (NS) based CPL materials using a chiral induced-synthesis strategy. Chiral amines served as chiral inducers to give COF TpBpy with chirality and participated in the modification of TpBpy, inhibiting the fluorescence quenching caused by π-π stacking to form ultrathin luminescent chiral COFs (chirCOFs) NS. The obtained chirCOFs R-/S-TpBpy NS had strong chirality and intense red CPL property with a |glum| of ∼0.02. Afterward, the carboxyl containing green and blue fluorescent dye molecules were postmodified onto the chirCOFs NS (chirCOFs/Dyes) to achieve color-adjustable CPL. Due to the chirality and energy transfer between chirCOFs and dye groups, the obtained chirCOFs/Dyes showed strong chirality and increased and tunable photoluminescence, exhibiting excellent, tunable, and amplified CPL performance with a maximum |glum| of ∼0.1, which was ∼5 times stronger than that of as-prepared chirCOFs NS. Moreover, the corresponding chirCOFs NS were dispersed into a polydimethylsiloxane (PDMS) matrix to form wafer size, highly transparent, and flexible COFs/PDMS films for practical CPL application. This study opens a new strategy to prepare ultrathin chirCOFs NS with strong and tunable CPL by chiral induction and provides a new approach for the preparation of transparent, large size, and flexible COFs composite films in chiral optical applications.

A Novel Cerium(IV)-Based Metal-Organic Framework for CO2 Chemical Fixation and Photocatalytic Overall Water Splitting.

Cerium (IV)-based metal-organic frameworks (MOFs) are highly desirable due to their unique potential in fields such as redox catalysis and photocatalysis. However, due to the high reduction potential of CeIV species in solution, it is still a great challenge to synthesize CeIV -MOFs with novel structures, which are extremely dominated by the hexanuclear Ce-O cluster inorganic building units (IBUs). Herein, a Ce-O IBU chain containing CeIV -MOF, CSUST-3 (CSUST: Changsha University of Science and Technology), was successfully prepared using the kinetic stabilization study of UiO-66(Ce)-NDC (H2 NDC=2,6-naphthalenedicarboxylic acid). Furthermore, owing to the superior redox activity, Lewis acidity and semiconductor-like behavior owing to Ce4+ , activated CSUST-3 was demonstrated to be an excellent catalyst for CO2 chemical fixation. One-pot synthesis of styrene carbonate from styrene and CO2 was achieved under mild conditions (1 atm CO2 , 80 °C, and solvent free). Moreover, activated CSUST-3 was shown to be a remarkable co-catalyst-free photocatalyst for overall water splitting (OWS), rendering 59 µmol g-1 h-1 of H2 and 22 µmol g-1 h-1 of O2 under simulated sunlight irradiation (Na2 S-Na2 SO3 as sacrificial agent).

Novel Third-Order Nonlinear Optical Materials with Craig-Möbius Aromaticity.

Electron delocalization in aromatic materials significantly impacts their third-order nonlinear optics (NLO). Despite organometallic complexes with Craig-Möbius aromaticity attracting great attention for their unusual physicochemical properties, their third-order NLO have been little studied to date. Herein, 12 Craig-Möbius aromatic organometallics with a stable structure similar to osmapentalyne, namely, carbolong complexes, are screened by DFT. They exhibit high third-order NLO responses because of the d and p electron delocalization in the organometallic ring. Furthermore, electron-hole distribution analyses draw a conclusion that extending the conjugated plane will increase the π-conjugation system to enhance the local excitation in the plane, and the introduction of typical aromatic ligands can result in the organometallic ring-to-ligand charge transfer (RLCT), which are effective methods to improve the third-order NLO response. This study opens a new window in the application of Craig-Möbius aromatic complexes and provides a new approach for third-order NLO materials design.

Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework Films for Giant Nonlinear Optical Limiting.

The development of metal-organic frameworks (MOFs) with nonlinear optical (NLO) properties is of pronounced significance for optical devices. Herein, a series of 2D MOFs ZnTPyP(M) (TPyP = 5,10,15,20-tetrakis(4-pyridyl)porphyrin, M = Cu, Ni, Mn, H2) films with [010]-orientation growth composed of ultrathin nanosheets from a pyridylporphyrinic ligand are first obtained by using a liquid-phase epitaxial (LPE) layer-by-layer (lbl) growth approach. ZnTPyP(M) films show a giant nonlinear optical limiting (OL) response and can be modulated by tuning the type of metalloporphyrinic ligands. As a result, ZnTPyP(Cu) film exhibits the highest nonlinear absorption coefficient of 5.7 × 10-6 m/W compared to other reported NLO materials. Density functional theory calculations were consistent with the experimental results, revealing that the tunable π-π* local excitation and the increased delocalization of the metalloporphyrinic group regulate the NLO performance of ZnTPyP(M) films. These findings provide new insight into the effect of 2D porphyrinic MOFs toward the NLO response and offer new film candidates for nonlinear OL application.

Surface chiroselective assembly of enantiopure crystalline porous films containing bichiral building blocks.

The development of chiral crystalline porous materials (CPMs) containing multiple chiral building blocks plays an important role in chiral chemistry and applications but is a challenging task. Herein, we report the first example of bichiral building block based enantiopure CPM films containing metal-organic cages (MOCs) and metal complexes. The functionalized substrate was immersed subsequently into homochiral metal complex (R)- or (S)-Mn(DCH)3 (DCH = 1,2-diaminocyclohexane) and racemic Ti4L6 cage (L = embonate) solutions by a layer-by-layer growth method. During the assembly process, the substrate surface coordinated with (R)- or (S)-Mn(DCH)3 can, respectively, layer-by-layer chiroselectively connect Δ- or Λ-Ti4L6 cages to form homochiral (R, Δ)- or (S, Λ)-CPM films with a preferred [111] growth orientation, tunable thickness and homogeneous surface. The resulting enantiopure CPM films show strong chirality, photoluminescence, and circularly polarized luminescence (CPL) properties as well as good enantioselective adsorption toward enantiomers of 2-butanol and methyl-lactate. The present in situ surface chiroselective strategy opens a new route to assemble homochiral CPM films containing multiple chiral building blocks for chiral applications.