Structures and conformations of 1-aryl-1,4-dihydro-3(2H)-isoquinolinones

The X-ray crystal structures of series of 1-aryl-1,4-dihydro-3(2H)-isoquinolinones (1-7) have been determined. Lactame heterocyclic ring possesses more or less deformed boat conformation in all examined structures. The aryl substituent adopts the equatorial position in the structures 1-3 and the axial one in 5-7. In the structure of 4, due to extremely flattened heterocyclic ring, aryl substituent location can be named as bisectional. In all solved structures the molecules are joined into the dimers via two N-H?O hydrogen bonds. At the same time, ¹H NMR studies in DMSO-d₆ solutions were accomplished and profound analysis of ²J, ³J, and ⁵J coupling constants have shown that in isoquinolinone system the heterocyclic ring adopts the boat conformation in all investigated compounds. The stereochemical orientations of the phenyl ring at C1 do not depend on the nature of the substituent but, exclusively, on the mode of substitution. However, three forms of undulated laktam heterocyclic ring conformation in respect of 1-aryl substituent positions were confirmed by calculation (conformational analysis).     

Uranium-sulfilimine chemistry. The preparation of Cp2*UCl2(HNSPh2) and its hydrolysis with HNSPh2 · H2O

The reaction of Cp₂*UCl₂ with HNSPh₂ produces Cp₂*UCl₂(HNSPh₂), which is the first structurally characterized complex of a sulfilimine. The hydrolysis of Cp₂*UCl₂(HNSPh₂) with HNSPh₂ · H₂O yields a tetrauranium cluster whose heavy atom structure has been determined by x-ray diffraction and which is formulated as a U^IV/U^V complex: [Cp*(Cl)(HNSPh₂)U(μ₃-O)(μ₂-O)₂U(Cl)(HNSPh₂)₂]₂.     

Solvothermal synthesis of new metal organic framework structures in the zinc-terephthalic acid-dimethyl formamide system

Two new metal organic framework (MOF) structures have been obtained from the Zn-terephthalic acid (H₂BDC)-dimethyl formamide (DMF) system and examined by single-crystal X-ray diffraction: Zn(C₈H₄O₄)(C₃H₇NO), 1, monoclinic C2/m, a=11.1369(5), b=14.0217(7), , β=106.316(1)°, , , Z=4, R₁=0.060, wR₂=0.169, S=1.27; Zn(HCO₂)₃(C₂H₈N), 2, trigonal , a=8.1818(1), , , , Z=6, R₁=0.014, wR₂=0.039, S=1.11. Contrary to previously published structures in the same system, the crystals were obtained by solvothermal synthesis at 381 K. Structure 1 consists of 2-D layers stacked in an offset manner to accommodate DMF moieties coordinated to Zn²⁺ within voids in adjacent layers. Structure 2 consists of a 3-D network constructed from Zn²⁺ ions bridged by deprotonated formic acid moieties. Over time, the structure of 1 rearranges to Zn(C₈H₄O₄)(C₃H₇NO)(H₂O) [monoclinic P2₁/n, a=6.6456(2), b=15.2232(5), , β=104.110(2)°, , , Z=4, R₁=0.048, wR₂=0.100, S=1.07], which is identical to the known MOF-2 structure, obtained by crystallization at ambient conditions. The three structures were determined from crystals with similar crystal habits picked from a single solvothermal synthesis batch. The study demonstrates that MOF syntheses can give not only multiple crystal structures under different conditions, but also that numerous different structures, including some that are metastable, can be formed under identical conditions.     

Role of structural flexibility in the fluorescence and photochromism of salicylideneaniline: the general scheme of the phototransformations

The mechanism of light-induced transformation in the salicylideneaniline molecule was studied by semiempirical PM3 calculations. The structures and energies of the minima and saddle points (transition states) on the S₀, S₁ and T₁ potential energy hypersurfaces (PESs) were obtained, together with the gradient lines on the PESs. The structure-energy scheme was compared with the experimental findings. According to the results obtained, the following principle processes are observed: fast S₁ excited state intramolecular proton transfer (ESIPT), followed by typical ESIPT fluorescence; the formation of two S₁ twisted intramolecular charge transfer (TICT) structures which quench the ESIPT fluorescence; the diabatic formation of two ground state metastable coloured “post-TICT” structures responsible for photochromism.     

Synthesis and Stereochemistry of New Bis(1,3-Oxathian-2-yl) Derivatives: Epimerisation and Chair–Twist Equilibria

The synthesis and stereochemistry of some new bis(1,3-oxathian-2-yl) derivatives are reported. The conformational behavior of these compounds and the orientation of their substituents are deduced from the NMR spectra, from the X-ray crystal structures of two compounds and from the ab-initio level calculations. The epimerization of diastereoisomers and the chair ⇌ 22,5-twist equilibria were studied by variable temperature NMR.     

Carbonat-isostere Anionen [SnX3]5− in den Verbindungen Rb6[SnX3]O0,5 und Cs6[SnX3]O0,5 mit X = As,Sb und Bi

Carbonate Isostructural Anions [SnX₃]^5? in the Compounds Rb₆[SnX₃]O_0.5 and Cs₆[SnX₃]O_0.5 with X = As, Sb, and Bi The metallic shining compounds Rb₆[SnX₃]O_0.5 and Cs₆[SnX₃]O_0.5 with X = As, Sb, and Bi were prepared from the melt starting from adequate mixtures of the elements and SnO₂. They crystallize in the hexagonal system (space group P6₃/mmc, No. 194, Z = 2) with the lattice constants mentioned in ?Inhaltsübersicht”?. In the structures of the isotypic compounds tin and the main group(V) elements build up trigonal planar anions [SnX₃]^5? with X = As, Sb, and Bi isostructural to the carbonate anion, oxygen forms isolated O^2? ions. The bond lengths Sn? X are significantly shortened with respect to the sums of Pauling covalent radii. The atoms of the units [SnX₃]^5? are coordinated by alkali metal cations forming trigonal prisms and the O^2? anions occupy octahedral holes.     

Direct preparation and structure determination of tertiary and secondary amine boranes from primary or secondary amine boranes

New secondary and tertiary amine borane derivatives were prepared in a one-pot reaction starting from primary amine boranes. The reaction involves treatment of an amine borane with 2 equivalents of s-BuLi at −78 °C. In general, mixtures of mono and di metallated products were obtained. Alkyl iodides and benzyl chloride reacted with the lithiated amine, but aldehydes and ketones were reduced. Conversion was high as determined by NMR, but moderate to low yields were obtained after chromatography, possibly due to decomposition on silica. Crystal structures were obtained for the compounds 3a, 3b and 3c.     

N,N,N′-Trialkyl-1,8-diaminonaphthalenes: convenient method of preparation from protonated proton sponges and the first X-ray information

A simple procedure for the synthesis of N,N,N′-trialkyl-1,8-diaminonaphthalenes is described. It consists in partial demethylation (dealkylation) of commercially available proton sponge [1,8-bis(dimethylamino)naphthalene] and some of its derivatives at heating with HBr-KI-DMF system. Limitation, scope and a possible mechanistic pathway for the reaction are discussed. For isomeric 8-dimethylamino-1-methylamino- and 1-dimethylamino-8-methylamino-4-nitronaphthalenes, X-ray measurements have been conducted. The first examples of complete realkylation reactions in the naphthalene proton sponges are reported.     

Negatively charged hyperbranched polyether-based polyelectrolytes

The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol⁻¹). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol⁻¹), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general.