RESUMO
Seven heterometallic iodoantimonates with the general formula (Cat)2{[Sb2M2I10]} (M = Cu(I) (1-6), Ag(I) (7)) were prepared. X-ray diffraction data indicate that these compounds are the first Sb(III) representatives of the structural type previously known only for heterometallic iodobismuthates(III). In 3 and 4, halogen-substituted cations form halogen bonds with the heterometallic halometalate chain. 1-7 show prominent thermal stability. The estimated optical band gaps lie between 2.16 and 2.40 eV. As in heterometallic iodobismuthates, incorporation of Cu+ rather than Ag+ provides a much lower band gap.
RESUMO
Nine heterometallic iodobismuthates with the general formula Cat2{[Bi2M2I10}] (M = Cu(I), Ag(I), Cat = organic cation) were synthesized. According to X-ray diffraction data, their crystal structures consisted of {Bi2I10} units interconnected with Cu(I) or Ag(I) atoms through I-bridging ligands, forming one-dimensional polymers. The compounds are thermally stable up to 200 °C. Optical band gaps (Eg), estimated at room temperature via diffuse reflectance measurements, range from 1.81 to 2.03 eV. Thermally induced changes in optical behavior (thermochromism) for compounds 1-9 were recorded, and general correlations were established. The thermal dependence of Eg appears to be close to linear for all studied compounds.
Assuntos
Cobre , Prata , Cobre/química , Prata/química , Difração de Raios X , Cátions/química , Polímeros/químicaRESUMO
Two isostructural pairs of supramolecular iodoantimonate(III) and iodobismuthate(III) complexes with I2 units "trapped" in solid state via halogen bonding-Cat3[[M2I9](I2)} (Cat = tetramethylammonium and 1-methylpyridinium, M = Sb(III) and Bi(III)) were prepared. For all compounds, values of optical band gaps were determined, together with thermal stability; the complexes were additionally characterized by Raman spectroscopy.
Assuntos
Antimônio , Bismuto , Antimônio/química , Bismuto/química , HalogêniosRESUMO
Reactions between bromoselenate(IV)-containing solutions, dibromine and salts of pyridinium-family organic cations resulted in structurally diverse, bromine-rich polybromine-bromoselenates(IV): (4-MePyH)5[Se2Br9][SeBr6](Br3)2 (1), (2-MePyH)2{[SeBr6](Br2)} (2), (PyH)2{[SeBr5]Br(Br2)2} (3), (1-MePy)2{[SeBr6](Br2)} (4). The compounds feature halogen and (in the case of 3) chalcogen bonding in solid state, resulting in formation of supramolecular architectures of different dimensionality. DFT calculations allowed estimation of the energies of non-covalent interactions in 1-4; additionally, characterization by Raman spectroscopy was performed.
RESUMO
Three supramolecular bromostannates(IV) with "trapped" diiodine molecules, Cat2{[SnBr6](I2)} (Cat = Me4N+ (1), 1-MePy+ (2) and 4-MePyH (3)), were synthesized. In all cases, I2 linkers are connected with bromide ligands via halogen···halogen non-covalent interactions. Articles 1-3 were studied using Raman spectroscopy, thermogravimetric analysis, and diffuse reflectance spectroscopy. The latter indicates that 1-3 are narrow band gap semiconductors.
Assuntos
Halogênios , Iodo , Halogênios/química , Ligação de Hidrogênio , Semicondutores , Análise Espectral RamanRESUMO
Reaction of SeO2 , tetramethylammonium (TMA) chloride, aqueous HCl and Cl2 yields oxochloroselenate with incorporated Cl2 units, TMA3 {[Se2 O2 Cl7 ](Cl2 )}. The main feature of this compound is the strong (up to 3.5â kcal mol-1 , according to DFT calculations) Clâ â â Cl bonding, which is also detected by Raman spectroscopy.
RESUMO
Supramolecular derivatives of chlorostannate(IV) and -plumbate(IV) with {Cl2} units, Cat2{[MCl6](Cl2)x} (1-5; M = Sn, Pb, cat = 1-methylpyridinium (1-MePy), tetramethylammonium (TMA)) were prepared and characterized by X-ray diffractometry and Raman spectroscopy. In particular, the TMA-containing complexes demonstrate remarkable thermal stability, releasing Cl2 only at elevated temperatures.
RESUMO
Reactions of [SbBr6]3- containing HBr solutions with bromide salts of 1,1'-(1,2-ethanediyl)bis(pyridine) (PyC22+) or 1,1'-(1,2-ethanediyl)bis(3,5-dimethylpyridine) (3,5-MePyC22+) initially result in the formation of the deep orange complexes Cat[SbBr5] (1 and 2), featuring unusual Sb···Br interactions in the solid state. In the mother liquor, 1 transforms into discrete binuclear (C2Py)2[Sb2Br10], which demonstrates polymorphism (triclinic 3 and monoclinic 4), while 2 transforms into polymeric (3,5-MePy){[SbBr4]} (5). DFT calculations reveal that the system of noncovalent Sb···Br contacts may be responsible for the appearance of the observed optical properties (unusual deep orange coloring).
RESUMO
One-dimensional iodine-rich iodobismuthates(III), Cat3{[Bi2I9](I2)3} [Cat = 1,4-MePy (1) and 1-EtBMAP (2)], feature the highest amount of "trapped" diiodine units in polyhalogen-halometalates of p-block elements. Both complexes have narrow optical band gaps (1.55 and 1.63 eV, respectively) and moderate thermal stability.
RESUMO
Unlike polyhalides of heavier halogens, polychlorides still remain exotic curiosities. Herein, we report preparation and investigation of complexes Cat2 {[TeCl6 ](Cl2 )} (cat=1-methylpyridinium (1) and tetramethylammonium (2)) where dichlorine units are "trapped" by chlorotellurate(IV) anions via a system of non-covalent Clâ â â Cl interactions. Complex 2 reveals a record thermal stability (>100 °C) for inclusion compounds with Cl2 , indications that such compounds can be used as solid Cl2 source.
RESUMO
Reactions of BiI3, I2, and iodide salts of two different pyridinum cations result in the formation of the novel iodine-rich iodobismuthates(III) (1,3-MePy)4{[Bi4I16](I2)} (1) and (1-MePy){[BiI4](I2)0.5) (2), where the halometalate anions are connected by diiodine linkers into one- or two-dimensional supramolecular structures. Both complexes reveal narrow optical band gaps and fairly high thermal stability, favoring their potential use in photovoltaic devices.