Investigation of Metastable Low Dimensional Halometallates

The solvothermal synthesis, structure determination and optical characterization of five new metastable halometallate compounds, [1,10-phenH][Pb3.5I8] (1), [1,10-phenH2][Pb5I12]·(H2O) (2), [1,10-phen][Pb2I4] (3), [1,10-phen]2[Pb5Br10] (4) and [1,10-phenH][SbI4]·(H2O) (5), are reported. The materials exhibit rich structural diversity and exhibit structural dimensionalities that include 1D chains, 2D sheets and 3D frameworks. The optical spectra of these materials are consistent with bandgaps ranging from 2.70 to 3.44 eV. We show that the optical behavior depends on the structural dimensionality of the reported materials, which are potential candidates for semiconductor applications.

The Isocyanide Complexes cis-[MCl2(CNC6H4-4-X)2] (M = Pd, Pt; X = Cl, Br) as Tectons in Crystal Engineering Involving Halogen Bonds

The isocyanide complexes cis-[MCl2(CNC6H4-4-X)2] (M = Pd; X = Cl, Br; M = Pt; X = Br) form isomorphous crystal structures exhibiting the Cl/Br and Pd/Pt exchanges featuring 1D chains upon crystallisation. Crystal packing is supported by the C–X···X–C halogen bonds (HaBs), C–H···X–C hydrogen bonds (HB), X···M semicoordination, and C···C contacts between the C atoms of aryl isocyanide ligands. The results of DFT calculations and topological analysis indicate that all the above contact types belong to attractive noncovalent interactions. A projection of the electron localization function (ELF) and an inspection of the electron density (ED) and the electrostatic potential (ESP) reveal the amphiphilic nature of X atoms playing the role of HaB donors, HaB and HB acceptors, and a nucleophilic partner in X···M semicoordination.

From Amorphous Silicones to Si-Containing Highly Ordered Polymers: Some Romanian Contributions in the Field

Polydimethylsiloxane (PDMS), in spite of its well-defined helical structure, is an amorphous fluid even at extremely high molecular weights. The cause of this behavior is the high flexibility of the siloxane backbone and the lack of intermolecular interactions attributed to the presence of methyl groups. These make PDMS incompatible with almost any organic or inorganic component leading to phase separation in siloxane-siloxane copolymers containing blocks with polar organic groups and in siloxane-organic copolymers, where dimethylsiloxane segments co-exist with organic ones. Self-assembly at the micro- or nanometric scale is common in certain mixed structures, including micelles, vesicles, et cetera, manifesting reversibly in response to an external stimulus. Polymers with a very high degree of ordering in the form of high-quality crystals were obtained when siloxane/silane segments co-exist with coordinated metal blocks in the polymer chain. While in the case of coordination of secondary building units (SBUs) with siloxane ligands 1D chains are formed; when coordination is achieved in the presence of a mixture of ligands, siloxane and organic, 2D structures are formed in most cases. The Romanian research group’s results regarding these aspects are reviewed: from the synthesis of classic, amorphous silicone products, to their adaptation for use in emerging fields and to new self-assembled or highly ordered structures with properties that create perspectives for the use of silicones in hitherto unexpected areas.

Sonochemical Synthesis of the Novel 1d Zig-zag Hg(Ii)-iodo Brigdged Metal-organic Coordination Compounds With Thiosemicarbazide Derivative Ligand

In the present research, a novel mercury (II) metal organic coordination compound, [Hg(Q)I2]n (Q = pyridine-4-carbaldehyde thiosemicarbazide) with nano rods shape was prepared applying an ultrasonic manner. The synthesized compound was determined with infrared spectroscopy (IR), scanning electron microscopy (SEM), and X-ray diffraction (XRD). In solid state the coordination polymer takes the appearance of a zig-zag 1D polymer. The coordination number of Hg (II) is four by one sulfur atom of organic ligand and three iodine atoms which two of iodine atoms are coordinated to other repeating units, and one of iodine is unattached. The zig-zag 1D chains interact with neighboring chains via poor interactions, making a 3D supramolecular metal organic polymer.

Attractive fluorine···fluorine interactions between perfluorinated alkyl chains: a case of perfluorinated Cu(II) diiminate Cu[C2F5–C(NH)–CF=C(NH)–CF3]2

A synthesis of the perfluorinated copper diiminate complex Cu[C2F5–C(NH)–CF=C(NH)–CF3]2 (3) and its self-assembly into infinite 1D chains in the crystal via Type II C(sp3)–F···F–C(sp3) contacts between perfluoroethyl substituents is reported. Rare Type II F···F interactions were studied by DFT calculations and topological analysis of the electron density distribution within the formalism of Bader’s theory (QTAIM method). This is the first report which discusses Type II contacts between perfuoroalkyl chains.

Coordination Polymers in Dicyanamido-Cadmium(II) with Diverse Network Dimensionalities

The synthesis and structural characterization of six dicyanamido-cadmium(II) complexes are reported: catena-[Cd(μ1,3-dca)(μ1,5-dca)(3-ampy)] (1), catena-[Cd3(μ1,3,5-dca)2(μ1,5-dca)4(pyNO)2(H2O)2] (2), catena-{Cd(H2O)2(μ1,5-dca)2](2,6-lut-NO)} (3), catena-[Cd(Me2en)(μ1,5-dca)2] (4), catena-[Cd(Me4en)(μ1,5-dca)2] (5), and [Cd(1,8-damnp)2(dca)2] (6), where dca = dicyanamide anion, 3-ampy = 3-aminopyridine, pyNO = pyridine-N-oxide, 2,6-lut-NO = 2,6-lutidine-N-oxide, Me2en = N,N-dimethyl-ethylenediamine, Me4en = N,N,N′,N′-tetramethyl-ethylenediamine, and 1,8-damnp = 1,8-diaminonaphthaline. The coordination polymers have different dimensionalities: 1 and 5 form 3D networks structures; 3 and 4 form polymeric 1D chains and 1DD double chains, respectively. Ribbons of three fused polymeric chains are observed in 2. In 6, the mononuclear complex units form a hydrogen-bonded supramolecular 3D network. In the coordination polymer compounds, the dca linkers display three bonding modes: the most common μ1,5-dca and the least popular μ1,3- and μ1,3,5-dca bonding. The luminescence emission and thermal properties of the complexes were investigated.

Construction of organometallic trefoil knots and one-dimensional chains featuring half-sandwich Cp*Rh corner units and an abnormal zwitterion ligand

An abnormal flexible O-coordinated zwitterion ligand L shows self-adaptive conformation behaviour in chemical self-assembly. Two trefoil knots were obtained with C-shaped ligand L and two novel 1D chains were obtained with Z-shaped ligand L.

A {Na2Fe10} isobutyrate cluster, interlinked into 1D chains

Charge-neutral [Na2Fe10O6(OH)4(isobutyrate)14(MeO)2(MeCN)2] coordination clusters, comprising a hollow ‘Chinese lantern’-like shell of six condensed planar triangular {FeIII3(μ3-O)} motifs, form upon ultrasonication of trinuclear Fe(III) isobutyrate units in acetonitrile in the presence...