Copper and silver heterometallic iodoantimonates: structure, thermal stability, and optical properties

Shentseva, Irina A.; Usoltsev, Andrey N.; Korobeynikov, Nikita A.; Sokolov, Maxim N.; Adonin, Sergey A.

doi:10.1039/d3dt02960c

Cited by 2 publications

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“…It solved in orthorhombic space group Pbcn , as half-independent. All Bi–I, Cu–I, and Cu–S bond lengths were within conventional ranges. − Bond angles around Bi were within 3° of 90° octahedral (O h ) and around Cu within 6.5° of 109.5° tetrahedral ( T d ). The structure is composed of O h BiI 6 units that are bridged to T d CuI 2 (THT) 2 units via pairs of μ 2 -I, forming via Cu(μ 2 -I) 2 Bi rhombs, see Figure .…”

Section: Resultsmentioning

confidence: 85%

“…A good deal of literature exists for charge-separated halobismuthate(III) and haloantimonate(III) salts, − ,,− much of it with alkali or organic ammonium cations. Additionally, there are multiple reports of halobismuthate and haloantimonate anions containing Cu(I) or Ag(I), such as Bi 2 Cu 2 I 10 2– , or paired with Cu(I) or Ag(I) cations, ,− many of which show relatively small band gaps. However, neutral ligand-supported iodobismuthate/cuprate and iodoantimonate/cuprate compounds remain extraordinarily rare.…”

Section: Introductionmentioning

confidence: 99%

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Ternary Complexes of BiI₃/CuI and SbI₃/CuI with Tetrahydrothiophene

Ballenger,

Giunta,

Carlson

et al. 2024

Inorg. Chem.

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Section: Resultsmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Ternary Complexes of BiI₃/CuI and SbI₃/CuI with Tetrahydrothiophene

Ballenger,

Giunta,

Carlson

et al. 2024

Inorg. Chem.

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Discrete Hexa- and Binuclear Heterometallic Iodobismuthate(III) Complexes with Cu(I) and Ag(I)

Shentseva,

Usoltsev,

Korobeynikov

et al. 2024

Inorg. Chem.

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The rare examples of discrete anionic halobismuthates(III) with group 11 elements were obtained. Those are (3-MePyH) 6 [Bi 4 Cu 2 I 20 ] (1) and (3,5-MePyC 6 ) 3 [BiAgI 7 ] 2 (2) (3-MePyH = 3-methylpyridinium cation, 3,5-MePyC 6 =1,6bis(3,5-dimethylpyridinium)hexane dication). Both complexes were isolated as pure phases; the optical band gaps for 1 and 2 are 1.75 and 2.23 eV, respectively. 1 features one of the lowest optical band gap values among Bi/ Cu clusters. ■ EXPERIMENTAL SECTION Starting Materials. All starting components (Bi 2 O 3 , CuI, Ag 2 O, and 2,6-diMePy) were purchased from commercial sources and used without purification. 1,6-Bis(3,5-dimethylpyridinium)hexane dibromide ({(3,5-diMePy)(CH 2 ) 6 (3,5-diMePy)}Br 2 ) was synthesized via reaction between 3,5-dimethylpyridine and corresponding 1,6dibromohexane in acetonitrile. All syntheses were conducted in air.In all experiments, concentrated HI was used.Synthesis of 1 and 2. For 1, 46.6 mg (0.1 mmol) of Bi 2 O 3 and 39 μL (0.3 mmol) of 3-methylpyridinium were mixed in 1 mL of concentrated HI. The resulting solution was evaporated to dryness. Nineteen mg of CuI (0.1 mmol) was added to the residue and was dissolved in 3 mL of acetonitrile/acetone mixture (1:1) upon heating at 70 °C for 1 h. After complete dissolution of reactants, the solution was slowly cooled to room temperature. In 24 h, dark-red crystals formed. Yield: 72%.For 2, 23.3 mg (0.05 mmol) of Bi 2 O 3 , 11.6 mg of Ag 2 O (0.05 mmol), and 45 mg (0.1 mmol) of (3,5-MePy) 2 (CH 2 ) 6 Br 2 were dissolved in 7 mL of concentrated HI and acetonitrile mixture (3:4) upon heating 70 °C for 1 h. After complete dissolution of reactants, the solution was slowly cooled to room temperature. In 24 h, orange crystals formed. Yield: 76%.X-ray Diffractometry. The diffraction data for 1 and 2 were collected on a Bruker D8 Venture diffractometer (0.5°ω-and φscans, fixed-χ three circle goniometer, CMOS PHOTON III detector, Mo−I□S 3.0 microfocus source, focusing Montel mirrors, λ =

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Copper and silver heterometallic iodoantimonates: structure, thermal stability, and optical properties

Abstract: Seven heterometallic iodoantimonates with the general formula (Cat)2{[Sb2M2I10]} (M = Cu(i) (1–6), Ag(i) (7)) were prepared.

Cited by 2 publications

References 50 publications

Ternary Complexes of BiI₃/CuI and SbI₃/CuI with Tetrahydrothiophene

Ternary Complexes of BiI₃/CuI and SbI₃/CuI with Tetrahydrothiophene

Discrete Hexa- and Binuclear Heterometallic Iodobismuthate(III) Complexes with Cu(I) and Ag(I)

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Copper and silver heterometallic iodoantimonates: structure, thermal stability, and optical properties

Abstract: Seven heterometallic iodoantimonates with the general formula (Cat)2{[Sb2M2I10]} (M = Cu(i) (1–6), Ag(i) (7)) were prepared.

Cited by 2 publications

References 50 publications

Ternary Complexes of BiI3/CuI and SbI3/CuI with Tetrahydrothiophene

Ternary Complexes of BiI3/CuI and SbI3/CuI with Tetrahydrothiophene

Discrete Hexa- and Binuclear Heterometallic Iodobismuthate(III) Complexes with Cu(I) and Ag(I)

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Product

Resources

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Ternary Complexes of BiI₃/CuI and SbI₃/CuI with Tetrahydrothiophene

Ternary Complexes of BiI₃/CuI and SbI₃/CuI with Tetrahydrothiophene