Li-based MOF-derived multifunctional PEO polymer solid-state electrolyte for lithium energy storage

A three-dimensional (3D) metal-organic framework containing Li-oxygen clusters, namely {[Li2(IPA)]·DMF}n (1) (H2IPA = isophthalic acid), has been constructed under solvothermal conditions. The Li-based MOF can be applied to lithium energy...

Luminescent Zn-MOF for detection of explosives and development of fingerprints

A luminescent 3D metal-organic framework [Zn(NDA)(AMP)] = PUC1 (where, NDA= naphthalene-2,6-dicarboxylic acid and AMP = 4-aminomethyl pyridine) was synthesized under solvothermal conditions. The synthesized 3D framework was fully characterized with...

Synthesis, structure and thermal stability of a mesoporous titanium(III) amine containing MOF with improved hydrogen sorption properties

The first mesoporous bimetallic TiIII/Al metal-organic framework (MOF) containing amine functionalities on its linkers has been selectively obtained by converting the cheap commercially available (TiCl3)3AlCl3 into Ti3-xAlxCl3(THF)3 and reacting this complex with 2-aminoterephthalic acid in DMF under soft solvothermal conditions. This compound is structurally related to the previously described NH2-MIL-101(M) (M = Cr, Al and Fe) MOFs. Thermal gravimetric analyses and in situ PXRD measurements demonstrated that this highly air-sensitive TiIII-containing MOF is structurally stable up to 200°C. Nuclear magnetic resonance (NMR) spectroscopy, elemental and inductively-coupled plasma (ICP) analyses revealed that NH2-MIL-101(TiIII) contains trinuclear Ti3(μ3-O)Cl(DMF)2(RCOO)6 clusters with strongly bound DMF molecules, and a small amount of aluminum. Sorption experiments reveal a higher affinity of this MOF for hydrogen compared to the previously described monometallic unfunctionalized MIL-101(TiIII) MOF.

Novel Lanthanide (III) Complexes Derived from an Imidazole–Biphenyl–Carboxylate Ligand: Synthesis, Structure and Luminescence Properties

A series of neutral mononuclear lanthanide complexes [Ln(HL)2(NO3)3] (Ln = La, Ce, Nd, Eu, Gd, Dy, Ho) with rigid bidentate ligand, HL (4′-(1H-imidazol-1-yl)biphenyl-4-carboxylic acid) were synthesized under solvothermal conditions. The coordination compounds have been characterized by infrared spectroscopy, thermogravimetry, powder X-ray diffraction and elemental analysis. According to X-ray diffraction, all the complexes are a series of isostructural compounds crystallized in the P2/n monoclinic space group. Additionally, solid-state luminescence measurements of all complexes show that [Eu(HL)2(NO3)3] complex displays the characteristic emission peaks of Eu(III) ion at 593, 597, 615, and 651 nm.

Syntheses, crystal structures, and fluorescent properties of three coordination polymers with 5-sulfoisophthalic acid anion and 4-phenylpyridine

Three coordination polymers—{[Ag2(SIP)(4-pp)]·[Ag(4-pp)2]·H2O}n, [Pb4(SIP)2( μ3-OH)2(H2O)2]n, and {[Zn2(SIP)2(4-pp)4][Zn(4-pp)2(H2O)4]·4H2O}n (SIP = 5-sulfoisophthalic acid anion, 4-pp = 4-phenylpyridine)—are constructed under hydrothermal or solvothermal conditions using sodium m-phthalate 5-sulfonate (NaH2SIP) and 4-phenylpyridine as ligands. The structures of the three complexes are determined by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analyses, Fourier-transform infrared analysis, and photoluminescence. The fluorescent properties of the complexes in the solid state are investigated at room temperature, and the results indicate that they all show photoluminescent properties.

A Multifunctional 3D Supermolecular Co Coordination Polymer With Potential for CO2 Adsorption, Antibacterial Activity, and Selective Sensing of Fe3+/Cr3+ Ions and TNP

A 3D supermolecular structure [Co3(L)2 (2,2′-bipy)2](DMF)3(H2O)3 1) (H3L = 4,4′,4″-nitrilotribenzoic acid) has been constructed based on H3L, and 2,2′-bipy ligands under solvothermal conditions. Compound 1 can be described as a (3, 6)-connected kgd topology with a Schläfli symbol (43)2(46.66.83) formed by [Co3(CO2)6] secondary building units. The adsorption properties of the activated sample 1a has been studied; the result shows that 1a has a high adsorption ability: the CO2 uptakes were 74 cm3·g−1 at 273 K, 50 cm3·g−1 at 298 K, the isosteric heat of adsorption (Qst) is 25.5 kJ mol−1 at zero loading, and the N2 adsorption at 77 K, 1 bar is 307 cm3 g−1. Magnetic measurements showed the existence of an antiferromagnetic exchange interaction in compound 1, besides compound 1 exhibits effective luminescent performance for Fe3+/Cr3+ and TNP.

Magnetism and Luminescence of a MOF with Linear Mn3 Nodes Derived from an Emissive Terthiophene-Based Imidazole Linker

A new terthiophene-based imidazole luminophore 5,5’-(1H-thieno[3,4-d]imidazole-4,6-diyl)bis(thiophene-2-carboxylic acid) (TIBTCH2, 5) was synthesized in one step from previously reported 4,6-di(thiophen-2-yl)-1H-thieno[3,4-d]imidazole (DTTI, 4), and their photophysical properties were studied and compared accordingly. Under solvothermal conditions, reacting 5 with Mn(OAc)2 yielded a new three-dimensional metal-organic framework (MOF, 6) which was structurally defined by single-crystal X-ray diffraction. In 6, all Mn(II) ions octahedrally bind to carboxylate-O atoms to form a linear Mn3 secondary building unit (SBU) that contains three distinct coordination modes. Importantly, 6 exhibits dual functional properties of ligand-based emission and metal-based magnetic behaviors.

Using Sound to Synthesize Covalent Organic Frameworks in Water

Most covalent organic frameworks (COFs) are synthesized using solvothermal conditions (>120 °C, >72 h) in harmful organic solvents. We report a strategy for rapidly synthesizing imine-linked COFs (< 60 min) in aqueous acetic acid using sonochemistry, avoiding most of the downsides of solvothermal methods. We first synthesized seven known COFs using this method and obtained crystallinity and porosity comparable to or better than materials from previously reported solvothermal routes. This sonochemical method even works in highly sustainable solvents, such as food-grade vinegar. The generality of the method was demonstrated by preparing two unreported COFs. Finally, we showed that one sonochemical COF is an excellent photocatalyst for sacrificial hydrogen evolution from water with a more sustained catalytic performance than its solvothermal analog. The speed, ease and generality of this sonochemical method with no sacrifice in material quality makes it an enabling methodology for rapid discovery of new functional COF materials.

Using Sound to Synthesize Covalent Organic Frameworks in Water

Most covalent organic frameworks (COFs) are synthesized using solvothermal conditions (>120 °C, >72 h) in harmful organic solvents. We report a strategy for rapidly synthesizing imine-linked COFs (< 60 min) in aqueous acetic acid using sonochemistry, avoiding most of the downsides of solvothermal methods. We first synthesized seven known COFs using this method and obtained crystallinity and porosity comparable to or better than materials from previously reported solvothermal routes. This sonochemical method even works in highly sustainable solvents, such as food-grade vinegar. The generality of the method was demonstrated by preparing two unreported COFs. Finally, we showed that one sonochemical COF is an excellent photocatalyst for sacrificial hydrogen evolution from water with a more sustained catalytic performance than its solvothermal analog. The speed, ease and generality of this sonochemical method with no sacrifice in material quality makes it an enabling methodology for rapid discovery of new functional COF materials.