Effect of basic site substituents on concerted proton-electron transfer in hydrogen-bonded pyridyl-phenols.

Separated concerted proton-electron transfer (sCPET) reactions of two series of phenols with pendent substituted pyridyl moieties are described. The pyridine is either attached directly to the phenol (HOAr-pyX) or connected through a methylene linker (HOArCH(2)pyX) (X = 4-NO(2), 5-CF(3), 4-CH(3), and 4-NMe(2)). Electron-donating and -withdrawing substituents have a substantial effect on the chemical environment of the transferring proton, as indicated by IR and (1)H NMR spectra, X-ray structures, and computational studies.

Synthesis, protonation, and reduction of ruthenium-peroxo complexes with pendent nitrogen bases.

Cyclopentadienyl and pentamethylcyclopentadienyl ruthenium(II) complexes have been synthesized with cyclic (RPCH(2)NR'CH(2))(2) ligands, with the goal of using these [Cp(R'')Ru(P(R)(2)N(R')(2))](+) complexes for catalytic O(2) reduction to H(2)O (R = t-butyl, phenyl; R' = benzyl, phenyl; R" = methyl, H). In each compound, the Ru is coordinated to the two phosphines, positioning the amines of the ligand in the second coordination sphere where they may act as proton relays to a bound dioxygen ligand. The phosphine, amine, and cyclopentadienyl substituents have been systematically varied in order to understand the effects of each of these parameters on the properties of the complexes.

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.

Poly[mu-2-aminopyrazine-kappa2N1:N4-mu-cyanido-copper(I)]: a three-dimensional network from laboratory powder diffraction data.

In the title compound, [Cu(CN)(C(4)H(5)N(3))](n) or [Cu(mu-CN)(mu-PyzNH(2))](n) (PyzNH(2) is 2-aminopyrazine), the Cu(I) center is tetrahedrally coordinated by two cyanide and two PyzNH(2) ligands. The Cu(I)-cyano links give rise to [Cu-CN](infinity) chains running along the c axis, which are bridged by bidentate PyzNH(2) ligands. The three-dimensional framework can be described as being formed by two interpenetrated three-dimensional honeycomb-like networks, both made of 26-membered rings of composition [Cu(6)(mu-CN)(2)(mu-PyzNH(2))(4)].

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).