Wood Cellulose Nanofibers Grafted with Poly(ε-caprolactone) Catalyzed by ZnEu-MOF for Functionalization and Surface Modification of PCL Films.

Renewable cellulose nanofiber (CNF)-reinforced biodegradable polymers (such as polycaprolactone (PCL)) are used in agriculture, food packaging, and sustained drug release. However, the interfacial incompatibility between hydrophilic CNFs and hydrophobic PCL has limited further application as high-performance biomaterials. In this work, using a novel as the catalyst, graft copolymers (GCL) with CNFs were grafted with poly(ε-caprolactone) (ε-CL) via homogeneous ring-opening polymerization (ROP), and used as strengthening/toughening nanofillers for PCL to fabricate light composite films (LCFs).

Defective Metal-Organic Frameworks with Tunable Porosity and Metal Active Sites for Significantly Improved Performance in Styrene Oxidation.

Metal active sites and sufficient porosity in metal-organic frameworks (MOFs) are crucial parameters determining the performances of catalysis, guest molecule adsorption, etc. Herein, through in situ introduction of Ru sites with different levels to Cu-BTC structure together with post-synthetic activation at 180 °C, a series of hierarchically porous CuRu-BTC (HP-CuRu-BTC) MOFs were obtained. Besides, selective thermal decomposition (STD) treatment was carried out at 240 °C to further tune the hierarchical pores and metal sites, yielding rare case of metal nanoparticles (NPs)@HP-CuRu-BTC composites.

Directing group strategies in rhodium-catalyzed C-H amination.

Construction of a carbon-nitrogen bond is one of the most prevalent operations in nature and organic synthesis. The resulting amino compounds are privileged structural fragments in natural products, pharmaceutical drugs, and functional materials. With the rapid advancement of C-H bond activation, directing-group strategies in C-H amination catalyzed by rhodium have emerged.

Copper mixed-triazolate frameworks featuring the thiophene-containing ligand towards enhanced photodegradation of organic contaminants in water.

By using a thiophene-containing triazole ligand -3,5-di(thiophen-2-yl)-1H-1,2,4-triazole (3,5-Th-tzH) and 3,5-diphenyl-1H-1,2,4-triazole (3,5-Ph-tzH) in different molar ratio in the reactant, copper(I) mixed-triazolate frameworks CuMtz-1 {[Cu(3,5-Ph-tz)(3,5-Th-tz)](BF)(CHOH)} (x = 0.5 for CuMtz-1a and 1.1 for CuMtz-1b) were firstly synthesized and characterized by PXRD, IR, H NMR, SEM, TG and UV-vis DRS.

Ultrahigh luminescence quantum yield lanthanide coordination polymer as a multifunctional sensor.

The investigation and development of advanced multifunctional and sensitive sensors with high luminescent quantum yield and the capability of detecting different analytes, such as metal ions, is imperative. Due to its inherent properties the lanthanide coordination complex is one candidate for sensing applications, particularly for multifunctional sensors. Herein, we present two series of alkali ion decorated lanthanide coordination polymers (Ln-CPs), which show ultrahigh luminescence quantum yields (QYs) of 77% (1a) and 92% (2a).

Highly Efficient Photocatalytic Degradation of Dyes by a Copper-Triazolate Metal-Organic Framework.

A copper(I) 3,5-diphenyltriazolate metal-organic framework (CuTz-1) was synthesized and extensively characterized by using a multi-technique approach. The combined results provided solid evidence that CuTz-1 features an unprecedented Cu tz cluster as the secondary building unit (SBU) with channels approximately 8.3 Å in diameter.

Encapsulation of Bimetallic Metal Nanoparticles into Robust Zirconium-Based Metal-Organic Frameworks: Evaluation of the Catalytic Potential for Size-Selective Hydrogenation.

The realization of metal nanoparticles (NPs) with bimetallic character and distinct composition for specific catalytic applications is an intensively studied field. Due to the synergy between metals, most bimetallic particles exhibit unique properties that are hardly provided by the individual monometallic counterparts. However, as small-sized NPs possess high surface energy, agglomeration during catalytic reactions is favored.

Simultaneous introduction of various palladium active sites into MOF via one-pot synthesis: Pd@[Cu3-xPdx(BTC)2]n.

Simultaneous incorporation of palladium within Pd-Pd and/or Pd-Cu paddlewheels as framework-nodes and Pd nanoparticle (NP) dispersion into MOF have been achieved for the first time via one-pot synthesis. In particular, the framework substitution of Cu(2+) by Pd(2+) as well as the pore loading with PdNPs have been confirmed and characterized by XPS. The obtained solids featuring such multiple Pd-sites show enhanced catalytic activity in the aqueous-phase hydrogenation of p-nitrophenol (PNP) with NaBH4 to p-aminophenol (PAP).

Ruthenium Metal-Organic Frameworks with Different Defect Types: Influence on Porosity, Sorption, and Catalytic Properties.

By employing the mixed-component, solid-solution approach, various functionalized ditopic isophthalate (ip) defect-generating linkers denoted 5-X-ipH2 , where X=OH (1), H (2), NH2 (3), Br (4), were introduced into the mixed-valent ruthenium analogue of [Cu3 (btc)2 ]n (HKUST-1, btc=benzene-1,3,5-tricarboxylate) to yield Ru-DEMOFs (defect-engineered metal-organic frameworks) of the general empirical formula [Ru3 (btc)2-x (5-X-ip)x Yy ]n . Framework incorporation of 5-X-ip was confirmed by powder XRD, FTIR spectroscopy, ultrahigh-vacuum IR spectroscopy, thermogravimetric analysis, (1) H NMR spectroscopy, N2 sorption, and X-ray absorption near edge structure. Interestingly, Ru-DEMOF 1 c with 32 % framework incorporation of 5-OH-ip shows the highest BET surface area (≈1300 m(2)  g(-1) , N2 adsorption, 77 K) among all materials (including the parent framework [Ru3 (btc)2 Yy ]n ).

Single-Molecule-Magnet Behavior in a [2 × 2] Grid Dy(III)4 Cluster and a Dysprosium-Doped Y(III)4 Cluster.

Thanks to the MeCN hydrolysis in situ reaction, a [2 × 2] square grid Dy(III)4 cluster based on a polypyridyl triazolate ligand, [Dy4(OH)2(bpt)4(NO3)4(OAc)2] (1), was separated successfully and characterized through single-crystal X-ray diffraction and SQUID magnetometry. The frequency-dependent signals in the out-of-phase component of the susceptibility associated with slow relaxation of the magnetization confirmed that complex 1 displays single-molecule magnet (SMM) behavior. Two distinct slow magnetic relaxation processes, with effective energy barriers Ueff1 = 93 cm(-1) for fast relaxation and Ueff2 = 143 cm(-1) for slow relaxation observed under a zero direct-current field, are mainly attributed to the origin of single-ion behavior, which can be further acknowledged by the magnetic investigation of a dysprosium-doped yttrium cluster.

The first {Dy4} single-molecule magnet with a toroidal magnetic moment in the ground state.

A toroidal magnetic moment in the absence of a conventional total magnetic moment was first observed in a novel tetranuclear dysprosium cluster with nonmagnetic ground state. The toroidal state is quite robust with respect to variations of the exchange parameters.