Inhaltsübersicht. Es wurden das Thioharnstoffderivat N,N-Diethyl-NЈ-2-naphthoylthioharnstoff (1) und drei N-(Dialkylaminothiocarbonyl)-NЈ-(1-naphthyl)-arylamidine (2-4) synthetisiert und mit diesen Cu II -, Ni II -und Pd II -Komplexe dargestellt. Die röntgenstrukturanalytischen Untersuchungen zeigen, daß 1 mit Cu II und Ni II unter Deprotonierung neutrale Bischelate von nahezu quadratischplanarer Koordination mit einer cis-Anordnung der O-und S-Liga-Abstract. The thiourea derivative N,N-diethyl-NЈ-2-naphthoylthiourea (1) and three N-(dialkylaminothiocarbonyl)-NЈ-(1-naphthyl)arylamidines (2-4) have been synthesized and Cu II -, Ni II -and Pd IIcomplexes of them have been prepared. According to the X-ray structure analyses 1 with Cu II and Ni II under deprotonation forms neutral bis-chelates of nearly square-planar coordination with a cis arrangement of the O and S ligator atoms. Using their N and S atoms in 1,3 position as ligators, 2-4 in deprotonated form coordi- EinleitungBei 2:1-Acylthioharnstoffmetallchelaten wird in der Regel cis-Koordination beobachtet. Bisher ist erst ein davon abweichender Ausnahmefall, nämlich das Naphthylgruppentragende trans -Bis(N,N-dibutyl-NЈ-1-naphthoylthioureato)platin(II) [1, 2], dargestellt und strukturell charakterisiert worden. Andererseits haben sich naphthylsubstituierte Liganden, die Schwefel-und Stickstoffatome als potentielle Ligatoratome enthalten, in jüngster Zeit für fluoreszenzanalytische Bestimmungen von umweltchemisch relevanten Schwermetallen [3, 4] und auch für die Anionenanalytik von Carbonat, Hydrogencarbonat und Hydrogenphosphat [5] als geeignet erwiesen. 1051 toratome bildet. 2-4 binden in deprotonierter Form über ihre Nund S-Atome in 1,3-Stellung an Cu II und Pd II zu neutralen Bischelaten Ϫ im Fall von Cu II mit verzerrt tetraedrischer Koordination. Pd II wird quadratisch-planar koordiniert und hat, offenbar aufgrund des sterischen Einflusses der 1-Naphthylgruppen, eine trans-Anordnung der N-und S-Ligatoratome.nate to Cu II and Pd II as neutral bis-chelates, in the case of Cu II with a distorted tetrahedral coordination. Pd II is coordinated square planar and has, probably due to the spatial influence of the 1-naphthyl groups, a trans arrangement of the N and S ligator atoms.

A new family of organic–inorganic hybrid layered materials based on cadmium and zinc sulfates was synthesized using 1,2-phenylenediamine (OPD), 1,3-phenylenediamine (MPD), and 1,4-phenylenediamine (PPD) as organic templates and ligands. The diamines act as structure-directing agents to obtain one-dimensional (1D), 2D, and 3D frameworks. Six new materials were obtained utilizing a simple, solvent-free synthesis approach: 1D: (OPD)2ZnSO4 1, (OPD)2CdSO4 2; 2D: (MPD)2ZnSO4 3, (MPD)2CdSO4 4; 3D: (PPD)­ZnSO4 5, (PPD)­CdSO4 6. The synthesis method proved to be scalable and robust. The crystal structures were determined using data from X-ray powder diffraction measurements (XRPD). It was observed that the type of amine determines the dimensionality of the obtained materials. 1D, 2D, and 3D structures were obtained using ortho-, meta-, and para-phenylenediamine isomers, respectively. The phase purity of the samples was confirmed by elemental analysis, and the morphology of the crystallites was studied using scanning electron microscopy. The thermal stability was determined by thermogravimetry and nonambient XRPD techniques. Additional characterization was performed for the two non-centrosymmetric, polar materials 3 and 4. Second-order nonlinear optical properties were examined using both experimental measurements (second harmonic generation) and theoretical calculations.

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Two organic-inorganic hybrid layered materials, namely poly [(-1,4-diaminobenzene-2 1, and poly[(-1,4-diaminobenzene-2 [Cu(SO 4 )(C 6 H 8 N 2 )] n , 2, have been synthesized using 1,4-phenylenediamine (PPD) as an organic template and component (linker). Both materials form three-dimensional frameworks. The crystal structures were determined using data from powder X-ray diffraction measurements. The purity and morphology of the compounds were studied by elemental analyses and SEM investigations, and their thermal stabilities were determined by thermogravimetric and nonambient powder X-ray diffraction measurements, which indicated that 1 is stable up to 537 K and 2 is stable up to 437 K.