Elastic films of single-crystal two-dimensional covalent organic frameworks.

The properties of polycrystalline materials are often dominated by defects; two-dimensional (2D) crystals can even be divided and disrupted by a line defect1-3. However, 2D crystals are often required to be processed into films, which are inevitably polycrystalline and contain numerous grain boundaries, and therefore are brittle and fragile, hindering application in flexible electronics, optoelectronics and separation1-4. Moreover, similar to glass, wood and plastics, they suffer from trade-off effects between mechanical strength and toughness5,6. Here we report a method to produce highly strong, tough and elastic films of an emerging class of 2D crystals: 2D covalent organic frameworks (COFs) composed of single-crystal domains connected by an interwoven grain boundary on water surface using an aliphatic bi-amine as a sacrificial go-between. Films of two 2D COFs have been demonstrated, which show Young's moduli and breaking strengths of 56.7 ± 7.4 GPa and 73.4 ± 11.6 GPa, and 82.2 ± 9.1 N m-1 and 29.5 ± 7.2 N m-1, respectively. We predict that the sacrificial go-between guided synthesis method and the interwoven grain boundary will inspire grain boundary engineering of various polycrystalline materials, endowing them with new properties, enhancing their current applications and paving the way for new applications.

Linker-Guided Growth of Single-Crystal Covalent Organic Frameworks.

The core features of covalent organic frameworks (COFs) are crystallinity and porosity. However, the synthesis of single-crystal COFs with monomers of diverse reactivity and adjustment of their pore structures remain challenging. Here, we show that linkers that can react with a node to form single-crystal COFs can guide other linkers that form either COFs or amorphous polymers with the node to gain single-crystal COFs with mixed components, which are homogeneous on the unit cell scale with controlled ratios. With the linker-guided crystal growth method, we created nine types of single-crystal COFs with up to nine different components, which are more complex than any known crystal. The structure of the crystal adapted approximately to that of the main component, and its pore volume could be expanded up to 8.8%. Different components lead to complex and diverse pore structures and offer the possibilities to gain positive synergies, as exemplified by a bicomponent COF with 2200 and 733% SO2 uptake capacity of that of the two pure-component counterparts at 298 K and 0.002 bar. The selectivity for separation of SO2/CO2 ranges from 1230 to 4247 for flue gas based on ideal adsorbed solution theory, recording porous crystals. The bicomponent COF also exhibits a 1300% retention time of its pure-component counterparts for SO2 in a dynamic column breakthrough experiment for deep desulfurization.

Fluorescence Thermometers Involving Two Ranges of Temperature: Coordination Polymer and DMSP Embedding.

The measurement of temperature is indispensable in the fields of life, science, and industry. Fluorescence thermometers are attractive to researchers because of their advantages such as noncontact, high sensitivity, fast response, and excellent anti-interference. Here, a new coordination polymer (HNU-76) was synthesized by assembling Zn2+ with the H3TCA ligand, a fluorescent molecule with an AIE behavior, which can be used as a fluorescence thermometer. At 100-210 K, the fluorescence intensity ratio of HNU-76 versus temperature conforms to an Arrhenius-type decay relationship (R2 = 0.997), which can be the candidate for low-temperature sensing. In order to increase the sensing range, 4-[4-(dimethylamino)styryl] pyndine (DMSP) was successfully embedded on HNU-76, obtaining HNU-76⊃DMSP. The fluorescence intensity of HNU-76⊃DMSP conforms to an Arrhenius-type decay relationship (R2 = 0.997) at 270-360 K versus temperature. HNU-76 can be used for fluorescence detection at low temperatures, due to the DMSP loading, and HNU-76⊃DMSP can serve as the temperature thermometer in a range of temperatures common. Both materials show good cyclability and have the potential to be used in fluorescence thermometers.

Single-phase white light material and antibiotic detection of lanthanide metal-organic frameworks.

WLEDs have been widely used in lighting and display equipment due to their energy-saving and environment-friendly advantages, but it is still a great challenge to construct high-quality single-phase white light materials for the preparation of WLEDs. In this work, three Ln-MOFs (HNU-82-84) with the same structure were synthesized by assembling rare earth ions (Tb3+, Eu3+, La3+) and 4,4',4''-nitrilotribenzoic acid (H3TCA) ligands. The structure and optical properties of the three compounds were investigated. Under the ultraviolet lamp, HNU-82-84 displays green light, red light, and blue light emission, respectively. Based on the RGB principle, aiming at the single-phase white material, the proportion of adding rare earth ions is reasonably adjusted to design and synthesize the Ln-MOF (Eu0.015Tb0.037La0.148-TCA) with CIE chromaticity coordinates of (0.319, 0.344). In addition, the WLED was prepared by Eu0.015Tb0.037La0.148-TCA and commercial LED lamps. Furthermore, HNU-82 has strong fluorescence emission and good water stability and can be used to detect nitrofurazone (NZF) and nitrofurantoin (NFT). The concentrations of the aqueous solutions of NZF and NFT had a well correlated linear relationship with the fluorescence quenching effect of HNU-82, and the detection limits were 6.60 × 10-7 mol L-1 and 4.62 × 10-7 mol L-1, respectively. Hence, HNU-82 also has potential as a fluorescent sensor for the detection of NZF and NFT in the aquatic environment.

Growth of single-crystal imine-linked covalent organic frameworks using amphiphilic amino-acid derivatives in water.

A core feature of covalent organic frameworks (COFs) is crystallinity, but current crystallization processes rely substantially on trial and error, chemical intuition and large-scale screening, which typically require harsh conditions and low levels of supersaturation, hampering the controlled synthesis of single-crystal COFs, particularly on large scales. Here we report a strategy to produce single-crystal imine-linked COFs in aqueous solutions under ambient conditions using amphiphilic amino-acid derivatives with long hydrophobic chains. We propose that these amphiphilic molecules self-assemble into micelles that serve as dynamic barriers to separate monomers in aqueous solution (nodes) and hydrophobic compartments of the micelles (linkers), thereby regulating the polymerization and crystallization processes. Disordered polyimines were obtained in the micelle, which were then converted into crystals in a step-by-step fashion. Five different three-dimensional COFs and a two-dimensional COF were obtained as single crystals on the gram scale, with yields of 92% and above.

Defect Healing of Micro/Nanocrystals via the Coordination Competition of Rare Earth in Crystal Engineering.

Defect engineering has been generally observed and utilized in crystal materials including metal oxides, metal-organic frameworks, and so on; however, how to relate the defect formation and crystallization process is needed to be revealed clearly, and how to heal the defect is a big challenge. Herein, based on the new coordination complex (HNU-53), the crystal defects were created by increasing the reaction time and crystal size. Following the crystal growth process, the crystal color centers were simultaneously generated, resulting in fluorescence quenching. To heal the defect, the crystal growth was controlled by the introduction of rare earth ions. With the coordination competition of rare earth ions, the crystal defects were reduced and recovery of fluorescence emission was achieved.

Dual-emitting piezofluorochromic dye@MOF for white-light generation.

An tetraphenylethylene-based MOF (HNU-49) has been synthesized, which exhibits interesting piezofluorochromic behavior. Additionally, rhodamine B (RhB) can be successful encapsulated in HNU-49, to emit the characteristic dual-emission of RhB and the framework. The combination of host-guest interaction and piezofluorochromism can precisely modulate the luminescence to achieve near white-light.

A Zinc Metal-Organic Framework for Concurrent Adsorption and Detection of Uranium.

Uranium is one of the principal raw materials in the nuclear industry, but if released into the natural environment, it also poses latent health risks to mankind. Therefore, there is an urgent need to develop a strategy that can concurrently detect and adsorb uranium to realize the sustainable development of nuclear power and protect the environment. In this work, a fluorescent zinc-based metal-organic framework (HNU-50) was designed and synthesized for the effective detection and extraction of U(VI). The amide groups on N-pyridin-4-ylpyridine-4-carboxamide ligands and two uncoordinated carboxyl oxygen atoms on pyromellitic acid ligands in HNU-50 provide potential uranium-binding sites. Consequently, HNU-50 is competent of selectively and efficiently catching uranyl ions, achieving an optimum adsorption capacity of 632 mg/g. Additionally, the adsorption of U(VI) results in fluorescence quenching of HNU-50, thus allowing sensitive and selective detection of U(VI) by fluorescence change. Note that HNU-50 exhibits a considerably low detection limit of 1.2 × 10-8 M for U(VI) in aqueous solution, which is below the World Health Organization maximum pollution standards for potable water (6.3 × 10-8 M).