The last two decades have witnessed significant progress in the design and synthesis of a new type of porous materials generally referred to as metal-organic frameworks (MOFs) and/or coordination polymers which can be readily selfassembled by the coordination of metal cations/clusters with organic linkers. Extensive efforts on such species have not only led to the creation of a huge number of MOFs of diverse topologies and aesthetic beauty, but also initiated a rational design strategy to construct porous materials with high surface areas, predictable structures, and tunable pore sizes to target some important applications, such as gas storage, separation, catalysis, magnetism, sensing, and imaging. Such progress within this field allows us to rationally design and synthesize porous MOFs with functional sites for specific host-guest recognition and thus to tune their functional properties.One of these extensively investigated methodologies is to immobilize unsaturated (open) Lewis acidic metal sites within porous MOFs for gas storage, catalysis, and sensing. [2][3][4][5] Immobilization of Lewis basic sites within porous MOFs, however, has been more challenging, as such Lewis basic sites tend to bind other metal ions to form condensed structures. The very few examples of porous MOFs with Lewis basic sites include POST-1 with pyridyl sites, [6] [Cd(4-btapa) 2 -(NO 3 ) 2 ]·6 H 2 O·2 DMF (4-btapa = 1,3,5-benzenetricarboxylic acid tris[N-(4-pyridyl)amide]) with amide sites [7] and [Zn 3 (OH) 3 (2-stp)(bpy) 1.5 (H 2 O)]·EtOH·2 H 2 O (2-stp = 2-sulfonylterephthalate; bpy = 4,4'-bipyridine) with anionic sulfonate sites.[ 6 and H 2 pdc in DMF at 120 8C over night. It was formulated as [Eu(pdc) 1.5 (dmf)]·(DMF) 0.5 -(H 2 O) 0.5 by elemental microanalysis and single-crystal X-ray diffraction studies, and the phase purity of the bulk material was independently confirmed by powder X-ray diffraction (PXRD) and thermal gravimetric analysis (TGA) (see the Supporting Information, Figure S1-3).Complex 1 is isostructural with [Er(pdc) 1.5 (dmf)]·(solv) n and [Y(pdc) 1.5 (dmf)]·(solv) n , in which Eu atoms are bridged by pdc organic linkers to form a three-dimensional rodpacking structure.[9] Each europium atom is coordinated by six oxygen atoms from the carboxylate groups of pdc, and capped by one distorted DMF molecule. One-dimensional hexagonal channels of about 6.3 8.5 along the a axis are filled by the capping DMF molecule, as well as free DMF and water molecules (Figure 1).TGA data indicated that 1 releases the free water and DMF, and terminal DMF molecules in the temperature range of 25-220 8C, to form a guest-free phase [Eu(pdc) 1.5 ] (1 a) which is thermally stable up to 450 8C. The powder X-ray diffraction (PXRD) pattern of the guest-free phase 1 a is almost identical with that of the as-synthesized 1, and matches well with that of the anhydrous [Er(pdc) 1.5 ], indicating that the basic 3D framework is retained and the in situ-generated open Eu sites are occupied by carboxylate oxygen atoms, thus the 1D hexagonal channe...

A luminescent metal-organic framework with small micropores for the enhanced recognition of Cu(2+) exhibits highly sensitive and selective sensing of Cu(2+) in aqueous solution.

The last two decades have witnessed significant progress in the design and synthesis of a new type of porous materials generally referred to as metal-organic frameworks (MOFs) and/or coordination polymers which can be readily selfassembled by the coordination of metal cations/clusters with organic linkers. Extensive efforts on such species have not only led to the creation of a huge number of MOFs of diverse topologies and aesthetic beauty, but also initiated a rational design strategy to construct porous materials with high surface areas, predictable structures, and tunable pore sizes to target some important applications, such as gas storage, separation, catalysis, magnetism, sensing, and imaging. Such progress within this field allows us to rationally design and synthesize porous MOFs with functional sites for specific host-guest recognition and thus to tune their functional properties.One of these extensively investigated methodologies is to immobilize unsaturated (open) Lewis acidic metal sites within porous MOFs for gas storage, catalysis, and sensing. [2][3][4][5] Immobilization of Lewis basic sites within porous MOFs, however, has been more challenging, as such Lewis basic sites tend to bind other metal ions to form condensed structures. The very few examples of porous MOFs with Lewis basic sites include POST-1 with pyridyl sites, [6] [Cd(4-btapa) 2 -(NO 3 ) 2 ]·6 H 2 O·2 DMF (4-btapa = 1,3,5-benzenetricarboxylic acid tris[N-(4-pyridyl)amide]) with amide sites [7] and [Zn 3 (OH) 3 (2-stp)(bpy) 1.5 (H 2 O)]·EtOH·2 H 2 O (2-stp = 2-sulfonylterephthalate; bpy = 4,4'-bipyridine) with anionic sulfonate sites.[ 6 and H 2 pdc in DMF at 120 8C over night. It was formulated as [Eu(pdc) 1.5 (dmf)]·(DMF) 0.5 -(H 2 O) 0.5 by elemental microanalysis and single-crystal X-ray diffraction studies, and the phase purity of the bulk material was independently confirmed by powder X-ray diffraction (PXRD) and thermal gravimetric analysis (TGA) (see the Supporting Information, Figure S1-3).Complex 1 is isostructural with [Er(pdc) 1.5 (dmf)]·(solv) n and [Y(pdc) 1.5 (dmf)]·(solv) n , in which Eu atoms are bridged by pdc organic linkers to form a three-dimensional rodpacking structure.[9] Each europium atom is coordinated by six oxygen atoms from the carboxylate groups of pdc, and capped by one distorted DMF molecule. One-dimensional hexagonal channels of about 6.3 8.5 along the a axis are filled by the capping DMF molecule, as well as free DMF and water molecules (Figure 1).TGA data indicated that 1 releases the free water and DMF, and terminal DMF molecules in the temperature range of 25-220 8C, to form a guest-free phase [Eu(pdc) 1.5 ] (1 a) which is thermally stable up to 450 8C. The powder X-ray diffraction (PXRD) pattern of the guest-free phase 1 a is almost identical with that of the as-synthesized 1, and matches well with that of the anhydrous [Er(pdc) 1.5 ], indicating that the basic 3D framework is retained and the in situ-generated open Eu sites are occupied by carboxylate oxygen atoms, thus the 1D hexagonal channe...

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A simple and effective aromatic nucleophilic monosubstitution reaction for the synthesis of aromatic amines via selective C–F bond cleavage of various fluoroarenes with primary and secondary aromatic amines is demonstrated.