Dong-Ying Du

A fluorescent sensor for highly selective detection of nitroaromatic explosives based on a 2D, extremely stable, metal-organic framework.

A 2D, extremely stable, metal-organic framework (MOF), NENU-503, was successfully constructed. It displays highly selective and recyclable properties in detection of nitroaromatic explosives as a fluorescent sensor. This is the first MOF that can distinguish between nitroaromatic molecules with different numbers of NO2 groups.

N-rich zeolite-like metal–organic framework with sodalite topology: high CO2 uptake, selective gas adsorption and efficient drug delivery

A novel zeolite-like metal–organic framework (ZMOF) with sodalite topology, [Zn(HL)]·DMA (IFMC-1, L = 4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazole and IFMC = Institute of Functional Material Chemistry), was solvothermally synthesized based on an N-rich aromatic ligand without a NH2 group. It exhibits high CO2 uptake and selective CO2/N2 adsorption capacity. For the first time, we investigated the influence of a large number of uncoordinated nitrogen atoms from aromatic rings for CO2 adsorption in ZMOFs. This result reveals that the high percentage of open N-donor sites leads to the high uptake capacity for CO2, even in the absence of any NH2 groups and open metal sites. In addition, it also exhibits efficient drug delivery capacity.

A Microporous Anionic Metal–Organic Framework for Sensing Luminescence of Lanthanide(III) Ions and Selective Absorption of Dyes by Ionic Exchange

Herein, a novel anionic framework with primitive centered cubic (pcu) topology, [(CH3 )2 NH2 ]4 [(Zn4 dttz6 )Zn3 ]⋅15 DMF⋅4.5 H2 O, (IFMC-2; H3 dttz=4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazole) was solvothermally isolated. A new example of a tetranuclear zinc cluster {Zn4 dttz6 } served as a secondary building unit in IFMC-2. Furthermore, the metal cluster was connected by Zn(II) ions to give rise to a 3D open microporous structure. The lanthanide(III)-loaded metal-organic framework (MOF) materials Ln(3+) @IFMC-2, were successfully prepared by using ion-exchange experiments owing to the anionic framework of IFMC-2. Moreover, the emission spectra of the as-prepared Ln(3+) @IFMC-2 were investigated, and the results suggested that IFMC-2 could be utilized as a potential luminescent probe toward different Ln(3+) ions. Additionally, the absorption ability of IFMC-2 toward ionic dyes was also performed. Cationic dyes can be absorbed, but not neutral and anionic dyes, thus indicating that IFMC-2 exhibits selective absorption toward cationic dyes. Furthermore, the cationic dyes can be gradually released in the presence of NaCl.

Stable Luminescent Metal–Organic Frameworks as Dual-Functional Materials To Encapsulate Ln3+ Ions for White-Light Emission and To Detect Nitroaromatic Explosives

A stable porous carbazole-based luminescent metal-organic framework, NENU-522, was successfully constructed. It is extremely stable in air and acidic/basic aqueous solutions, which provides the strategy for luminescent material encapsulation of Ln(3+) ions with tunable luminescence for application in light emission. More importantly, Ln(3+)@NENU-522 can emit white light by encapsulating different molar ratios of Eu(3+) and Tb(3+) ions. Additionally, Tb(3+)@NENU-522 is found to be useful as a fluorescent indicator for the qualitative and quantitative detection of nitroaromatic explosives with different numbers of -NO2 groups, and the concentrations of complete quenching are about 2000, 1000, and 80 ppm for nitrobenzene, 1,3-dinitrobenzene, and 2,4,6-trinitrophenol, respectively. Meanwhile, Tb(3+)@NENU-522 displays high selectivity and recyclability in the detection of nitroaromatic explosives.

Polyoxometalate-based crystalline tubular microreactor: redox-active inorganic–organic hybrid materials producing gold nanoparticles and catalytic properties

Here, we synthesize a novel polyoxometalate-based crystalline tubular inorganic–organic compound, Mn[Zn(im)]2{[Na(H2O)]2[Mn(H2O)2][Zn(im)2][P4Mo6O31H6]2}·8H2O (IFMC-100) (im and IFMC correspond to imidazole and Institute of Functional Material Chemistry, respectively). Au-anchored tubular microreactor, Au@IFMC-100, has been prepared by simple immersion of IFMC-100 in an ethanol solution of HAuCl4 without any extra reducing agents, photochemical and electrochemical auxiliaries. Furthermore, IFMC-100 and Au@IFMC-100 have been employed as catalysts for the reduction of K3Fe(CN)6 and 4-nitrophenol with NaBH4 in aqueous solution, respectively. The results indicate the as-prepared Au@IFMC-100 microtubes exhibit enhanced catalytic performance in redox catalysis.

A Stable Porous Anionic Metal–Organic Framework for Luminescence Sensing of Ln3+ Ions and Detection of Nitrobenzene

A hexagonal channel-based porous anionic metal-organic framework was successfully constructed. IFMC-3 is stable in air and acidic/basic aqueous solutions at room temperature, and constitutes a selective luminescent sensing material for Ln(3+) ions and a recyclable probe for the sensitive detection of nitrobenzene.

A multifunctional microporous anionic metal–organic framework for column-chromatographic dye separation and selective detection and adsorption of Cr3+

In this work, a novel microporous anionic metal–organic framework (MOF), [Zn(ABTC)0.5(NO3)][(CH3)2NH2]·DMA·3H2O (NENU-505; NENU = Northeast Normal University; H4ABTC = 3,3′,5,5′-azobenzenetetracarboxylic acid; DMA = N,N-dimethylacetamide), has been rationally synthesized under solvothermal conditions. Single-crystal X-ray analysis reveals that NENU-505 is a (4,4)-connected 3D network with pts topology. Charge neutrality is achieved by [(CH3)2NH2]+ ions. It is noteworthy that NENU-505 displays high stability in air for more than two months. In particular, the adsorption ability of NENU-505 toward ionic dyes has been also investigated. According to the UV/vis spectroscopy analysis and the colour variance of NENU-505, we found that the cationic dyes could be efficiently adsorbed over a period of time, while the neutral and anionic dyes could not be adsorbed. Therefore, NENU-505 exhibits selective adsorption toward cationic dyes and can potentially serve as a column-chromatographic filler for the separation of dye molecules. Furthermore, the cationic dyes can be gradually released in the presence of NaCl. More interestingly, when NENU-505 was immersed in different metal ion DMA solutions, it performs as a rare example of a highly selective and sensitive sensor for Cr3+ ions. In connection to this, the probable sensing mechanism was also further investigated in detail in this paper. Remarkably, this is the first MOF to exhibit an excellent ability for the detection and adsorption of Cr3+ ions in a convenient, economical, and environmentally friendly manner.

Self‐Assembly versus Stepwise Synthesis: Heterometal–Organic Frameworks Based on Metalloligands with Tunable Luminescence Properties

A new family of heterometal-organic frameworks has been prepared by two synthesis strategies, in which IFMC-26 and IFMC-27 are constructed by self-assembly and IFMC-28 is obtained by stepwise synthesis based on the metalloligand (IFMC=Institute of Functional Material Chemistry). IFMC-26 is a (3,6)-connected net and IFMC-27 is a (4,8)-connected 3D framework. The metalloligands {Ni(H4 L)}(NO3 )2 are connected by binuclear lanthanide clusters giving rise to a 2D sheet structure in IFMC-28. Notably, IFMC-26-Eux Tby and IFMC-28-Eux Tby have been obtained by changing the molar ratios of raw materials. Owing to the porosity of IFMC-26, Tb(3+) @IFMC-26-Eu and Eu(3+) @IFMC-26-Tb are obtained by postencapsulating Tb(III) and Eu(III) ions into the pores, respectively. Tunable luminescence in metal-organic frameworks is achieved by the two kinds of doping methods. In particular, the quantum yields of heterometal-organic frameworks are apparently enhanced by postencapsulation of Ln(III) ions.

Derivation and Decoration of Nets with Trigonal-Prismatic Nodes: A Unique Route to Reticular Synthesis of Metal–Organic Frameworks

Quests for advanced functionalities in metal-organic frameworks (MOFs) inevitably encounter increasing complexity in their tailored framework architectures, accompanied by heightened challenges with their geometric design. In this paper, we demonstrate the feasibility of rationally exploiting topological prediction as a blueprint for predesigned MOFs. A new triangular frusta secondary building unit (SBU), {Zn4(tz)3}, was bridged by three TDC(2-) fragments to initially form a trigonal prismatic node, {Zn8(tz)6(TDC)3} (Htz = 1H-1,2,3-triazole and H2TDC = 2,5-thiophenedicarboxylic acid). Furthermore, the trigonal prism unit can be considered as a double SBU derived from triply bound triangular frusta. By considering theoretical derived nets for linking this trigonal-prismatic node with ditopic, tritopic, and tetratopic linkers, we have synthesized and characterized a new family of MOFs that adopt the decorated lon, jea, and xai nets, respectively. Pore sizes have also been successively increased within TPMOF-n family, which facilitates heterogeneous biomimetic catalysis with Fe-porphyrin-based TPMOF-7 as a catalyst.

A stable metal–organic framework with suitable pore sizes and rich uncoordinated nitrogen atoms on the internal surface of micropores for highly efficient CO2 capture

An air-stable tetrazolate-containing framework, [Zn2L2]·2DMF (NENU-520, H2L = 4-(1H-tetrazole-5-yl)biphenyl-4-carboxylic acid), with uncoordinated N atoms on its internal surface was solvothermally synthesized and structurally characterized. This metal–organic framework (MOF) exhibited high CO2 uptake of 79.9 cm3 cm−3 at 298 K and 100 kPa, as well as excellent adsorption selectivity for CO2 over CH4 and N2. Particularly, its exceptionally high selectivity of CO2 over N2 at 298 K has ranked NENU-520 among the highest MOFs for selective CO2 separation. Furthermore, the potential application of NENU-520 for the fixed bed pressure swing adsorption (PSA) separation of CO2 from CH4 and N2 has been validated via simulated breakthrough experiments. The small channel with the size of 3.6 A, combined with CO2-accessible free nitrogen atoms directed toward the inner surface, is believed to contribute to its high CO2 uptake capacity and selectivity. Thus, this work represents a unique way to target MOF materials for highly selective CO2 separation by incorporating CO2-philic functional sites on pore surfaces, and at the same time optimizing pore sizes.