ABSTRACT
In order to demonstrate the role of the fluorination and some solvents in the structural organization of the Ag(I) coordination polymers with ß-diketonate ligands (R1C(O)CαHC(O)R2)- we synthesized a series of the compounds containing tfac- (R1 = CH3, R2 = CF3) and pfpac- (R1 = CH3, R2 = C2F5) anions. Solvent-free [Ag(L)]∞ (L = tfac 1, pfpac 2) compounds and the corresponding acetonitrile and toluene adducts have been characterized by elemental analysis and/or NMR, IR and single-crystal XRD. This series includes five new coordination polymers. Compound 1 is a 3D coordination framework based on Ag-Ochelate/bridge, Ag-Cα bonds, and argentophilic interactions. An increase in the fluorinated group leads to a chain coordination polymer 2 of an unusual structural organization. These chains can be represented as a "DNA-type", where two intertwined helices based on Ag-Ochelate and Ag-Cα bonds are connected through Ag-Obridge ones. Two structural types of chain coordination polymers, [Ag(tfac)(CH3CN)] and [Ag2(L)2(solvent)], have been revealed for the adducts. The latter structural type differs significantly from the previously studied toluene and acetonitrile adducts of fluorinated Ag(I) ß-diketonates of the same stoichiometry. Thermal analysis in helium showed that both 1 and 2 decompose to metallic silver with the compound of pfpac-ligand being slightly more stable.
ABSTRACT
New data on the thermodynamic properties of the melting and sublimation of a series of volatile iridium(i) complexes [Ir(cod)(L)] with cyclooctadiene-1,5 (cod) and ß-diketones (L = RC(O)CHC(O)R') have been obtained with differential scanning calorimetry and vapor pressure measurements. Combining experimental, empirical and theoretical methods, ways to estimate difference in heat capacities between gas and crystal phases have been suggested. An effect on the volatility in introducing the simplest alkyl, fluorinated alkyl and aryl terminal groups (R and R') into the chelate ligand has been explained in terms of a detailed crystal packing analysis supported by a quantum chemical calculation of crystal lattice energies. To reveal the influence of the coordination center, the thermal behavior of complexes was compared with that for the tris-chelates, [Ir(L)3]. The study broadens our understanding of relationships between the structure and thermal properties of volatile precursors, which is useful for further tuning effective compounds for metal-organic chemical vapor deposition purposes.
ABSTRACT
The title compounds, 4-(diiodoarsanyl)benzoic acid, (I), and 3-(diiodoarsanyl)benzoic acid, (II), both [As(C(7)H(5)O(2))I(2)], which possess a -COOH coordinating group, form molecular crystal structures composed of hydrogen-bonded dimers, the packing differences of which are caused by the relative position of the diiodoarsanyl groups. The para isomer, with Z' = 1, crystallizes in a layered structure with shortened contacts of the As atoms to only the arene rings of adjacent molecules. In contrast, the meta isomer, with Z' = 3, forms separate rectangular blocks of three ribbons, each composed of dimeric molecular units positioned almost directly above each other and with the As atoms possessing only two As···I contacts to the I atoms of neighbouring molecules.
ABSTRACT
The first monomeric anhydrous scandium tris(8-quinolinolate) complex 1 with the 2-amino-8-quinolinolate ligands and the Sc(2)Q(6) dinuclear complex 2 with the unsubstituted 8-quinolinolate ligands have been synthesized and characterized by X-ray analysis and DFT calculations. The intramolecular hydrogen bonds appear to be responsible for the unique monomeric structure of complex 1. The DFT-based analysis of the electron density topology reveals the (3,-1) critical points corresponding to the O···H and N···H bonds. The two scandium atoms in compound 2 are inequivalent due to different ligand surroundings. They are coordinated by seven (5O, 2N) and eight (4O, 4N) ligand atoms. The increase in the coordination number is accompanied by a decrease in the positive charge of the metal atom as evidenced by the DFT calculations.
