Use of a "Shoe-Last" Solid-State Template in the Mechanochemical Synthesis of High-Porosity RHO-Zinc Imidazolate.

We report the first use of a nonionic solid (NIS) as a template in mechanosynthesis of a metal-organic framework. Through eight intermolecular C-H···O hydrogen bonds, the macrocyclic MeMeCH2 template predictably functions as a "shoe-last" for the assembly of double-eight rings in the liquid-assisted reaction of ZnO and imidazole (ImH). The resulting new form of ZnIm2 (namely xMeMeCH2@RHO-Zn16Im32) is available in multigram amounts, highly porous, and thermally stable.

Reproducible Synthesis and High Porosity of mer-Zn(Im)2 (ZIF-10): Exploitation of an Apparent Double-Eight Ring Template.

Reproducible synthesis of the elusive merlinoite (mer) topology of zinc imidazolate (mer-Zn(Im)2, or ZIF-10) has been achieved by employing a simple macrocyclic solute-MeMeCH2-as a kinetic template. The corresponding phase-pure material, mer-MeMeCH2@Zn16(Im)32, is confirmed to be porous and exhibits one of the highest experimental surface areas (1893 m(2)/g, BET) yet reported for any ZIF. The X-ray single crystal structure of mer-MeMeCH2@Zn16(Im)32·xsolvent reveals the role of the macrocyle as an 8-fold hydrogen bond acceptor in templating the requisite double-eight rings (d8r) of the mer framework.

Reversible luminescent reaction of amines with copper(I) cyanide.

Copper(i) cyanide exposed to various liquid or vapor-phase amines (L) at ambient temperature produces a variety of visible photoluminescence colors via reversible formation of amine adducts. The adducts show phase matches to authentic (CuCN)L(n), n = 0.75-2.0, produced by heating CuCN with liquid amine.

Structural and NMR characterization of Sm(III), Eu(III), and Yb(III) complexes of an amide based polydentate ligand exhibiting paramagnetic chemical exchange saturation transfer abilities.

Complexes of Sm(III), Eu(III), and Yb(III) with a new polydentate ether ligand with amide arms were synthesized. Solid state X-ray structures of the complexes reveal all three complexes crystallize in monoclinic unit cells. The mononuclear complexes have nine coordinate tricapped trigonal prismatic geometries with coordination of all four amide carbonyl oxygen and all three of the backbone ether oxygen atoms. The molecules possess a pseudo C(2) symmetry axis. The complexes were characterized by solution and solid state emission spectroscopy and IR spectroscopy. Solution state behavior of the complexes was further explored using NMR. The (1)H NMR spectra show 16 peaks suggesting the complexes are slow in exchanging on the NMR time scale and that the C(2) symmetry axis is maintained. The NMR spectra were assigned using (1)H, (13)C, COSY, and HMQC experiments. The Eu(III) complex was tested for the recently explored Magnetic Resonance Imaging phenomenon called paramagnetic chemical exchange saturation transfer (PARACEST). At physiological pH and temperature two CEST peaks were observed that caused a decrease in the bulk water molecule signal intensity of 10 and 16%.

Copper(I) cyanide networks: synthesis, structure, and luminescence behavior. Part 2. Piperazine ligands and hexamethylenetetramine.

A variety of photoluminescent, and in some cases thermochromic, metal-organic networks of CuCN were self-assembled in aqueous reactions with amine ligands: (CuCN) 2(Pip) ( 1a), (CuCN) 20(Pip) 7 ( 1b), (CuCN) 7(MePip) 2 ( 2), (CuCN) 2(Me 2Pip) ( 3a), (CuCN) 4(Me 2Pip) ( 3b), (CuCN) 7(EtPip) 2 ( 4), (CuCN) 4(Et 2Pip) ( 5), (CuCN) 3(BzPip) 2 ( 6a), (CuCN) 5(BzPip) 2 ( 6b), (CuCN) 7(BzPip) 2 ( 6c), (CuCN) 4(BzPip) ( 6d), (CuCN) 2(Bz 2Pip) ( 7), (CuCN)(Ph 2CHPip) ( 8a), (CuCN) 2(Ph 2CHPip) ( 8b), (CuCN) 3(HMTA) 2 ( 9a), (CuCN) 5(HMTA) 2 ( 9b), and (CuCN) 5(HMTA) ( 9c) (Pip = piperazine, MePip = N-methylpiperazine, Me 2Pip = N, N'-dimethylpiperazine, EtPip = N-ethylpiperazine, Et 2Pip = N, N'-diethylpiperazine, BzPip = N-benzylpiperazine, Bz 2Pip = N, N'-dibenzylpiperazine, Ph 2CHPip = N-(diphenylmethyl)piperazine, and HMTA = hexamethylenetetramine). New X-ray structures are reported for 1b, 2, 3b, 4, 5, 6a, 6d, 7, 8b, 9b, and 9c. An important structural theme is the formation of (6,3) (CuCN) 2(piperazine) sheets with or without threading of independent CuCN chains. Strong luminescence at ambient temperature is observed for all but complexes 6 and 7. All luminescent compounds show a broad emission band in the blue region at about 450 nm attributable to metal-to-ligand charge transfer behavior based on the large Stokes shift between excitation and emission maxima. 3, 8, and 9 are thermochromic due to an additional lower energy emission band, which is absent at 77 K.

Threaded structure and blue luminescence of (CuCN)20(Piperazine)7.

The structurally unique and highly luminescent 20 : 7 complex of CuCN with piperazine (Pip) was formed under aqueous conditions; its structure reveals two interpenetrated 2D sub-networks in 6 : 1 ratio: (CuCN)2(Pip) and (CuCN)8(Pip), the latter consisting of Cu18(CN)16(Pip)2 macrocycles.

Copper(I) cyanide networks: synthesis, luminescence behavior and thermal analysis. Part 1. Diimine ligands.

Metal-organic networks of CuCN with diimines (L) = pyrazine (Pyz), 2-aminopyrazine (PyzNH(2)), quinoxaline (Qox), phenazine (Phz), 4,4'-bipyridyl (Bpy), pyrimidine (Pym), 2-aminopyrimidine (PymNH(2)), 2,4-diaminopyrimidine (Pym(NH(2))(2)), 2,4,6-triaminopyrimidine (Pym(NH(2))(3)), quinazoline (Qnz), pyridazine (Pdz), and phthalazine (Ptz) were studied. Open reflux reactions produced complexes (CuCN)(2)(L) for L = Qox, Phz, Bpy, PymNH(2), Pym(NH(2))(2), Qnz, and Pdz and (CuCN)(3)(L) complexes for L = Pyz, PyzNH(2), Qox, Bpy, Pym(NH(2))(3), and Pdz. Also produced were (CuCN)(3)(Pyz)(2), (CuCN)(PyzNH(2)), (CuCN)7(Pym)(2), (CuCN)(5)(Qnz)(2) and (CuCN)(5)(Ptz)(2). X-ray structures are presented for (CuCN)(2)(Pdz), (CuCN)(2)(PymNH(2)), and (CuCN)(7)(Pym)(2). Hydrothermal reactions yielded additional X-ray structures of (CuCN)(2)(PyzNH(2)), (CuCN)(3)(Pym(NH(2))(2)), (CuCN)(4)(Qnz), a second (CuCN)(2)(Pdz) phase, (CuCN)(5)(Pdz)2, (CuCN)(2)(Ptz), and (CuCN)(7)(Ptz)2. Structural trends, including cuprophilic interactions and cyano-bridged Cu(2)(CN)(2) dimer formation, are discussed. Particularly short Cu...Cu interactions are noted for the novel 4- and 5-coordinate Cu(2)(CN)(2) dimers. Thermal analyses show that most of the complexes decompose with loss of L around 160-180 degrees C. Luminescence behavior is relatively weak in the products.