Alois Popitsch

Synthesis and luminescence properties of mesostructured thin films activated by in-situ formed trivalent rare earth ion complexes

Incorporation of trivalent rare earth ions and 1,10-phenanthroline into mesostructured block-copolymer/silica thin films produces spectrally pure emission from in-situ formed rare earth ion complexes.

Preparation and structural characterization of catena-μ(1,3)-azido-μ(O,N-picolinato)-aquamanganese(II), Mn(NC5H4CO2)(N3)(H2O)

Abstract A mixed ligand complex of manganese(II) azide with picolinic acid, namely catena-μ(1,3)-azido-μ(O,N-picolinato)aquamanganese(II), was synthesized and characterized by X-ray crystallography. The coordination environment of the manganese(II) atom is a distorted octahedron. Each metal atom, which links a water molecule [MnO(1) = 2.218(3) A], is chelated by a picolinato anion [via its ring nitrogen atom, MnN = 2.278(3) A, and a carboxylato oxygen atom, MnO(2) = 2.167(2) A]. The chelating carboxylate O(2) atom is further bridging another manganese atom giving rise to a centrosymmetric dimeric Mn2O2 [MnO(2a) = 2.243(2) A]. These dimeric units are connected to μ(1,3) bridging azido ligands [MnN = 2.167(3) and 2.219(3) A] to form a two dimensional layer structure along the ab plane. Each water molecule forms two OH···O hydrogen bonds with the non-chelating carboxylate oxygen atoms of two adjacent picolinato groups. The IR and Raman spectra are also reported and correlated with the structure of the complex. The vibrational bands of diagnostic value are compared to the values of the carboxylic acid and the free anion.

Synthesis, spectral and structural characterization of a bridging chloro complex of manganese(II) with picolinic acid ; [Mn(C5H4NCO2H)(C5H4NCO2)Cl]2

Abstract The title compound of manganese(II) with picolinic acid was synthesized and characterized by spectroscopic and X-ray crystallographic methods. In the structure of the complex [Mn(C5H4NCO2H)(C5H4NCO2)Cl]2 each manganese(II) atom is coordinated by two nitrogen atoms at MnN distances of 2.268(6) A and two carboxylic oxygen atoms O(1) at MnO bond lengths of 2.191(4) A, belonging to two picolinato groups. The Cl− anions act as bridging ligands to build edge-sharing dimeric Mn2Cl2 units [MnCl = 2.500(2) A with the Mn⋯Mn separation of 3.608(2) A and Cl⋯Cl separation of 3.462(1) A. The four-membered dimeric Mn2Cl2 rings are planar and oriented along the c-axis of the unit cell. The O(2)⋯O(2) separation between non-coordinated carboxylate oxygen atoms of adjacent dimeric coordination polyhedra is 2.423(7) A. The IR and Raman spectral results confirm the existence of neutral picolinic acid as well as the picolinate anion. The vibrational bands of diagnostic value are compared with the values of the carboxylic acid and the free anion.

SYNTHESIS AND SPECTRAL AND STRUCTURAL CHARACTERIZATION OF A BRIDGING CHLOROPICOLINATOCOPPER(II) COMPLEX, CU(C5H4NCOO)CL

SummaryThe title complex of copper(II) chloride with picolinic acid was prepared and characterized by spectroscopic and X-ray crystallographic methods. The complex, Cu(C5H4NCOO)Cl, crystallizes tetragonal, space group P42/n (No. 86),a=976.4(1),c=1499.6(4) pm,N=8;Rw=0.048 for 543 observed MoKα diffractometer data. In the structure of the complex two μ-chloro bridges form only slightly bent Cu2Cl2 rings [Cu-Cl=224.2(4) and 275.6(4) pm] with Cu...Cu separation of 359.4(2) pm and Cl...Cl separation of 348.7(5) pm. These edge-sharing copper coordination polyhedra are further linked via the N and O donor atoms of the picolinato anions at Cu-N distances of 199.6(12) pm and Cu-O bond lengths of 195.7(8) and 200.6(10) pm, to form a two-dimensional layer structure in which these layers are arranged along theab plane. Each picolinate anion functions as a tetra-dentate ligand: N(1) and O(2) are coordinated to the same Cu(II) center whereas O(1) is bonded to a neighbouring Cu(II) center. O(2) is further bonded to the latter Cu(II) center at a long Cu-O distance of 256.5(8) pm. The electronic, infrared and Raman spectra of the solid complex are reported and discussed.ZusammenfassungDer Titelkomplex aus Kupfer(II)chlorid und Picolinsäure wurde dargestellt und mit spektroskopischen und Röntgen-Einkristall-Methoden charakterisiert. Cu(C5H4NCOO)Cl kristallisiert tetragonal, Raumgruppe P42/n (No. 86),a=976.4(1),c=1499.6(4) pm,N=8;Rw=0.048 für 543 beobachtete Mokα-Diffraktometerdaten. In der Kristallstruktur bilden zwei μ-chloro-Brücken nur wenig gewinkelte Cu2Cl2-Ringe aus [Cu-Cl=224.2(4) und 275.6(4) pm], mit Cu...Cu Abständen von 359.4(2) pm und Cl...Cl Abständen von 348.7(5) pm. Die kantenverknüpften Koordinationspolyeder der Kupferatome sind in Richtung derab-Ebene über die N- und O-Donoratome der Picolinat-Anionen [mit Cu-N Abständen von 199.6(12) pm und Cu-O Abständen von 195.7(8) und 200.6(10) pm] zu einer zweidimensionalen Schichtstruktur verknüpft. Jedes Picolinat-Anion fungiert als vierzähniger Ligand: N(1) und O(2) sind zum selben Cu(II)-Zentrum gebunden; O(1) ist zum benachbarten Cu(II)-Zentrum koordiniert, zu dem O(2) einen langen Cu-O-Abstand von 256.5(8) pm ausbildet. Die elektronischen, Infrarot- und Raman-Spektren des Festkörper-Komplexes werden berichtet und diskutiert.

Kristallstruktur von Monosilber(I)amidosulfat, AgSO3NH2

A crystal structure analysis of the colourless AgSO3NH2 was carried out at room temperature:M=203.95, orthorhombic, Pcab,a=7.809 (2) Å,b=8.067 (2) Å,c=11.682 (3) Å,V=735.9 Å3,Z=8,dx=3.681 Mgm−3,F(000)=760, Mo Kα, λ=0.71069 Å (graphite monochromator), μ=5.77 mm−1,R=4.36% (509 reflections, 56 parameters). The ionic structure shows approximate trigonal bipyramidal coordination around the Ag+-ions.

Kristallstruktur von Sulfamid, SO2(NH2)2

X-ray crystal structure analyses of sulfamide were carried out at 293 K and at 100 K:M=96.10, orthorhombic, Fdd2,Z=8,F(000)=400, Mo Kα, λ=0.71069 Å (graphite monochromator). A) 293 K:a=9.127 (1) Å,b=16.857 (5) Å,c=4.579 (1) Å,V=704.50 Å3,dx=1.812 Mgm−3, μ=0.648 mm−1,R=1.77%,Rw=1.94% (384 reflections, 33 parameters). B) 100K:a=9.059 (1) Å,b=16.780 (8) Å,c=4.517 (1) Å,V=686.63 Å3,dx=1.859 Mgm−3, μ=0.665 mm−1,R=1.78%,Rw=1.95% (404 reflections, 33 parameters). The sulfamide molecule shows at 293 K S-O and S-N distances of 1.429 (1) Å and 1.620 (1) Å, respectively, which are in agreement with IR data. Hydrogen positions could be determined from differenceFourier syntheses. Strong weakening of some intense low order reflections by extinction was observed, their anisotropy depends on the crystal and on temperature.

Chelatbildende Enaminoketone I. Synthese von unsymmetrischen Liganden

Syntheses of chelating enaminoketones for a potential use in enrichment or recovery of metals from their aqueous solutions are described. Tridentate ligands were prepared either from aromatic amines, triethoxymethane and cyclic 1,3-dicarbonyl compounds in a one-step synthesis, or from the anilinomethylene compounds obtained by this approach and aliphatic amines. Polymerizable ligands have also been synthesized by reaction with (meth)acryloyl chloride and copolymerized with styrene to yield a chelating polymer.

Intermolecular interactions of inorganic and organic molecules embedded in zeolite-type materials probed by near-infrared Fourier transform Raman spectroscopy

Abstract Near-infrared Fourier transform Raman spectroscopy represents an excellently suited tool to investigate spectroscopically inorganic and organic molecules occluded in zeolite-type materials as well as interactions between them. Two examples are presented: First, insertion compounds of iodine in various microporous SiO 2 modifications (deca-dodecasil 3R, all-silica theta-1 and silicalite-1) are discussed. Intermolecular interaction between the inserted molecules is prevented by occlusion of iodine in the cages of deca-dodecasil 3R, but is allowed in the insertion compounds of hosts with higher pore dimensionalities. The intermolecular coupling is confirmed by an appreciable reduction of the Raman shifts, as observed similarly for liquid and amorphous iodine. The second example deals with pyridine and n -alkylamines ( n -propyl-, n -butyl- or n -pentylamine) occluded during synthesis in all-silica ferrierite. Raman spectra reveal for all compounds, regardless of the n -alkylamine used, an interaction between the n -alkylamine and neighboring pyridine molecules, with both amines being located in the ten-membered ring channels. For this reason, it is proposed that bimolecular complexes, consisting of an n -alkylamine weakly bound to a pyridine molecule act as structure-directing agents during synthesis.

Schwingungsspektroskopische Untersuchungen an Sulfamid-Einkristallen

The infrared (300 K) andRaman (300 and 90 K) spectra of single crystals of sulfamide are recorded. In addition theRaman spectra of the deuterated and N15-substituted polycrystalline sulfamide are measured. A vibrational assignment based on these data and a normal coordinate analysis is proposed. Lattice bands and factor group splittings are discussed.

Kristallstruktur von Trisilber(I)amidosulfat-3-Ammoniak-2-Wasser, Ag3SO3N · 3NH3 · 2H2O

An X-ray crystal structure analysis of colourless Ag3SO3N · 3NH3 · 2H2O was carried out at room temperature:M=504.79, orthorhombic, P212121,a=6.275 (1) Å,b=11.826 (2) Å,c=14.299 (12) Å,V=1061.10 Å3,Z=4,dx=3.160 Mgm−3,F(000)=940, Mo Kα, λ=0.71069 Å (graphite monochromator), μ=5.60 mm−1,R=4.71%,Rw=4.96% (982 reflections, 120 parameters). The structure consists of Ag ribbons; each Ag atom is linearly co-ordinated to two N atoms with distances corresponding to covalent Ag-N bonds; no Ag-O coordination is observed; the N atom of the SO3N group is surrounded by three Ag atoms; compared to amidosulfuric acid, the SO3N group shows significant deformation.