Structural Information on Supramolecular Copper(II) β-Diketonate Complexes from Atomic Force Microscopy and Analytical Ultracentrifugation.

Supramolecular Cu(II) complexes were prepared from two trifunctional β-diketone ligands. The ligands (CHSi(phacH) and CHSi(phprH), represented by LH) contain three aryl-β-diketone moieties joined by an organosilicon group. The complexes have the empirical formula CuL, as expected for combinations of Cu and L.

A copper complex of an unusual hy-droxy-carboxyl-ate ligand: [Cu(bpy)(CHO)].

A copper(II) complex, (2,2'-bi-pyridine-κ ,')[2-hy-droxy-2-(hy-droxy-methyl-κ)propane-dioato-κ , ]copper(II), [Cu(CHO)(CHN)], containing the unusual anionic chelating ligand 2-(hy-droxy-meth-yl)tartronate, has been synthesized. [Cu(bpy)(NO)](NO) was mixed with ascorbic acid and Dabco (1,4-di-aza-bicyclo-[2.2.

Two isomers of [1-benzyl-4-(pyridin-2-yl-κ)-1-1,2,3-triazole-κ ]di-chlorido-bis-(dimethyl sulfoxide-κ)ruthenium(II).

The structures of two isomers of the title compound, [RuCl(CHN)(CHOS)], and , are reported. Isomers and are produced by reaction of the pyridyl-triazole ligand 1-benzyl-4-(pyridin-2-yl)-1-1,2,3-triazole (bpt) () with -[RuCl(DMSO-)(DMSO-)]. Reaction in acetone produces 95% , which is the -6-14 isomer, with DMSO and chlorido ligands, and 5% (the -6-32 isomer, with DMSO and chlorido ligands, and the pyridyl moiety of bpt to DMSO).

Externally and Internally Functionalized Copper(II) β-Diketonate Molecular Squares.

Five functionalized bis(β-diketones) and their Cu(II) molecular squares are described. The new bis(β-diketones), m-pbhxH2 (3), 5-MeO-m-pbaH2 (4), 5-BuO-m-pbaH2 (5), 2-MeO-m-pbaH2 (6), and 2-MeO-m-pbprH2 (7), were prepared by reaction of the corresponding aldehydes with phospholenes, as we previously reported for m-pbaH2 (1) and m-pbprH2 (2). Ligand 3 has long alkyl chains in its β-diketone moieties, while ligands 4-7 have alkoxy substituents on their aromatic rings.

Tris(4-formyl-phen-yl)phosphane oxide tetra-hydro-furan hemisolvate.

The title compound, C21H15O4P·0.5C4H8O, contains an ordered phosphane oxide in a general position and a tetra-hydro-furan solvent mol-ecule disordered about a twofold axis. All three aldehyde substituents are nearly coplanar with their attached benzene rings, with C-C-C-O torsion angles in the range 1.

Cyclic pyridyltriazole-Cu(II) dimers as supramolecular hosts.

Tetradentate bis(pyridyltriazole) ligands containing aromatic spacers of different sizes react with Cu(2+) to produce metallo-supramolecular hosts that bind 1,4-diazabicyclo[2.2.2]octane molecules internally.

μ(2)-m-Xylylenebis(salicylaldiminato)-bis-(η(4)-1,5-cyclo-octa-diene)dirhodium(I) dichloro-methane solvate.

In the title solvate, [Rh(2)(C(22)H(18)N(2)O(2))(C(8)H(12))(2)]·CH(2)Cl(2), each organometallic mol-ecule is composed of two Rh(I) cations, the tetra-dentate dianion α,α'-bis-(salicylaldiminato)-m-xylene and two 1,5-cyclo-octa-diene (COD) ligands. Each Rh(I) atom is coordinated by one O atom [Rh-O = 2.044 (2) and 2.

Bis(o-phenylenebis(acetylacetonato))dicopper(II): a strained copper(II) dimer exhibiting a wide range of colors in the solid state.

The bis(β-diketone) o-pbaH(2) (o-phenylenebis(acetylacetone), 1) reacts readily with Cu(2+). Although this reaction was expected to yield a trimeric product (2) on geometric grounds, the binuclear complex Cu(2)(o-pba)(2) (3) is obtained instead. Materials containing Cu(2)(o-pba)(2) adopt a variety of colors, depending on the solvents used in preparation: dark green (microcrystalline, 3a), golden-brown (ansolvous, 3b), green-brown (CHCl(3)-C(6)H(6) solvate, 4), dark blue (nitrobenzene solvate, 5), or violet (toluene solvate, 6).

Preparation of an isocyano-beta-diketone via its metal complexes, by use of metal ions as protecting groups.

A ligand containing isocyanide and beta-diketone functional groups, 3-(4-isocyanophenyl)-2,4-pentanedione (HacphNC), and several of its metal complexes have been prepared. The free isocyano-beta-diketone could not be prepared by dehydration of the analogous formamide, HacphNHCHO, because of the reactivity of its beta-diketone moiety. Instead, the metal complexes Al(acphNC)(3), Fe(acphNC)(3), Cu(acphNC)(2), and Zn(acphNC)(2) were synthesized by dehydration of the formamido-beta-diketonate complexes Al(acphNHCHO)(3), Fe(acphNHCHO)(3), Cu(acphNHCHO)(2), and Zn(acphNHCHO)(2).

A nanoporous Ag-Fe mixed-metal-organic framework exhibiting single-crystal-to-single-crystal transformations upon guest exchange.

The reaction of solutions of Fe(Pyac)3 [PyacH=3-(4-pyridyl)-2,4-pentanedione] and AgNO3 produces two types of porous mixed-metal-organic frameworks (M'MOFs). With lower AgNO3 concentrations, the product (M'MOF1) has a 2D honeycomb structure with Ag:Fe=1:1 and pores of ca. 12x16 A.

trans-Dichloridotetrakis(3,5-dimethylpyridine)copper(II).

The title compound, [CuCl(2)(C(7)H(9)N)(4)], lies on a site of crystallographic 42 (D(4)) symmetry in the space group P4/nnc, and is isomorphous with the Ni and Co analogues. The Cu and Cl atoms thus lie on a fourfold axis, and the 3,5-lutidine ligands lie on twofold axes. The Cu-Cl distance is 2.

Porous Cu-Cd mixed-metal-organic frameworks constructed from Cu(Pyac)2 [Bis[3-(4-pyridyl)pentane-2,4-dionato]copper(II)].

Porous Cu-Cd mixed-metal-organic frameworks [[Cd(NO(3))(2)](2)[(Cu(Pyac)(2)](3)] (M'MOF 1) and [[CdCl(2)][Cu(Pyac)(2)](2)] (M'MOF2) [Cu(Pyac)(2) = bis[3-(4-pyridyl)pentane-2,4-dionato]copper(II)] have been synthesized by the reaction of Cu(Pyac)(2) with Cd(NO(3))(2) and CdCl(2). They are noninterpenetrating 1D ladder and 2D square-grid frameworks, constructed from Cu(Pyac)(2) building blocks with T-shaped Cd(NO(3))(2) nodes and square-planar CdCl(2) nodes, respectively. The 1D ladders and 2D square grids are stacked in ABCABC.

Flexible cofacial binuclear metal complexes derived from alpha,alpha-bis(salicylimino)-m-xylene.

The tetradentate Schiff-base ligand SIXH2 (alpha,alpha-bis(salicylimino)-m-xylene), prepared from salicylaldehyde and m-xylylenediamine, forms cofacial binuclear complexes with Pd and Cu. Of the two isomers possible (trans-syn and trans-anti) for M2(SIX)2, these complexes crystallize exclusively as the trans-anti isomer. In ansolvous Pd2(SIX)2, the metal-containing planes are approximately parallel, with PdPd 4.

3-(4-cyanophenyl)pentane-2,4-dione and its copper(II) complex.

The beta-diketone 3-(4-cyanophenyl)pentane-2,4-dione crystallizes as the enol tautomer 4-(2-hydroxy-4-oxopent-2-en-3-yl)benzonitrile, C(12)H(11)NO(2), (I), with an intramolecular O-H.O hydrogen bond [O.O = 2.

Solvent-dependent 4(4) square grid and 6(4).8(2) NbO frameworks formed by Cu(Pyac)2 (bis[3-(4-pyridyl)pentane-2,4-dionato]copper(II)).

The title compound crystallizes from anhydrous solvents in a simple square-grid topology, but when water is present, crystals form with an unusual interpenetrated 3D NbO topology whose pores contain hydrogen-bonded solvent molecules.

Structures of anhydrous and hydrated copper(II) hexafluoroacetylacetonate.

Crystal structure analyses are reported for anhydrous copper(II) hexafluoroacetylacetonate (Cu(hfac)(2)) and for two of its hydrates. The anhydrous compound (Cu(hfac)(2), 1: P1; at 100 K, a = 5.428(1), b = 5.

Electronic Absorption Spectra and Phosphorescence of Oxygen-Containing Molybdenum(IV) Complexes.

Electronic absorption and emission spectra are reported for salts of two oxomolybdenum(IV) cations, [MoOCl(CN-t-Bu)(4)](+) and [MoOCl(Ph(2)PCH(2)CH(2)PPh(2))(2)](+), and for the new Mo(IV) complex [trans-Mo(OCH(3))(2)(CN-t-Bu)(4)](2+). All three ions show absorption bands (lambda(max,abs) 550-570 nm; epsilon 45-120 M(-)(1) cm(-)(1)) attributable to the (1)A(1)[(d(xy)())(2)] --> (1)E[(d(xy)())(1)(d(xz)()(,)(yz)())(1)] (C(4)(v)()) transition, and the last two show weak shoulders in the 700-750 nm range due to the analogous spin-forbidden ((1)A(1) --> (3)E) transition. Phosphorescence (lambda(max,em) 850-960 nm) occurs in the solid state for all three compounds at both room temperature and 77 K, and for [MoOCl(CN-t-Bu)(4)](+) in CH(2)Cl(2) at room temperature.

Phosphorescence and Structure of a Tetrameric Copper(I)-Amide Cluster.

The colorless copper(I) cluster [CuN(Si(CH(3))(3))(2)](4), which contains a square-planar Cu(4)N(4) core, phosphoresces in CH(2)Cl(2) solution (lambda(max), 512 nm; lifetime, 30 &mgr;s) and in the solid state at room temperature. Its electronic absorption spectrum in CH(2)Cl(2) consists of two intense bands at 283 and 246 nm; these transitions, as well as the phosphorescence, are likely to involve population of MOs reflecting substantial Cu.Cu interactions.

Solution Photophysics, One-Electron Photooxidation, and Photoinitiated Two-Electron Oxidation of Molybdenum(III) Complexes.

Several six-coordinate Mo(III) complexes phosphoresce and undergo photooxidation in room-temperature solution. The phosphorescence of (Me(3)[9]aneN(3))MoX(3) (Me(3)[9]aneN(3) = 1,4,7-trimethyl-1,4,7-triazacyclononane) in CH(3)CN at room temperature occurs with the following maxima, lifetimes, and quantum yields: X = Cl, 1120 nm, 1.0 &mgr;s, and 6.

A New Binucleating Ligand Based on Anthracene and Its Cofacial Dirhodium(I) and Diiridium(I) Complexes.

A new bis(beta-keto enamine) ligand (2a, ABIH(2)) containing a 1,8-anthracenediyl bridging group has been synthesized by a four-step procedure that relies on the Pd-catalyzed cross-coupling between (3,5-dimethylisoxazol-4-yl)trialkyltin and 1,8-dibromoanthraquinone or -anthracene. The molecular structures of the 1,8-bis(3,5-dimethylisoxazol-4-yl)anthraquinone (8) and -anthracene (10) intermediates were determined by X-ray analysis. Crystal data for 8: orthorhombic, space group Pbca; a = 14.