10.1021/ic9516370.s001
Casey C. Raymond
Casey C.
Raymond
Peter K. Dorhout
Peter K.
Dorhout
Synthesis, Characterization, and Bonding of Two New Heteropolychalcogenides:
α-CsCu(S<i><sub>x</sub></i>Se<sub>4-<i>x</i></sub>) and CsCu(S<i><sub>x</sub></i>Se<sub>6-<i>x</i></sub>)
American Chemical Society
1996
polyselenide salts
band gap
CsCuQ 6 structures
Heteropolychalcogenide salts
compound
polychalcogenide geometry
hydrothermal reaction conditions
cesium chloride
sulfur analog
CsCuS 1.6 Se 4.4
structures display
Extended H ückel crystal
site distribution
CsCuQ 6 phase
selenium phases
copper metal
sulfur atoms
absorption spectra
lattice parameters
reaction products
P 2 1 2 1 2 1
1996-09-11 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Synthesis_Characterization_and_Bonding_of_Two_New_Heteropolychalcogenides_-CsCu_S_i_sub_x_sub_i_Se_sub_4-_i_x_i_sub_and_CsCu_S_i_sub_x_sub_i_Se_sub_6-_i_x_i_sub_/3615324
The Cs−Cu−Q (Q = S, Se) system has been investigated using
copper metal, cesium chloride, and alkali-metal
polychalcogenide salts under mild hydrothermal reaction conditions.
Heteropolychalcogenide salts and mixtures
of known polysulfide and polyselenide salts have been used as reagents.
The reaction products contain the
α-CsCuQ<sub>4</sub> and CsCuQ<sub>6</sub> structures. The
α-CsCuQ<sub>4</sub> phase exhibits a smooth transition in lattice
parameters from
the pure sulfur to the pure selenium phases, based on Vegard's law.
The CsCuQ<sub>6</sub> phase has been prepared as the
pure sulfur analog and a selenium rich analog. The single-crystal
structures of the disordered compounds
α-CsCuS<sub>2</sub>Se<sub>2</sub> (<i>P</i>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub>,
<i>Z</i> = 4, <i>a</i> = 5.439(1) Å, <i>b</i> =
8.878(2) Å, <i>c</i> = 13.762(4) Å) and
CsCuS<sub>1.6</sub>Se<sub>4.4</sub> (<i>P</i>1̄,
<i>Z</i> = 2, <i>a</i> =
11.253(4) Å, <i>b</i> = 11.585(2) Å, <i>c</i> =
7.211(2) Å, α = 92.93°, β = 100.94°, γ =
74.51°) have been solved using
a correlated-site occupancy model. These disordered structures
display a polychalcogenide geometry in which
the sulfur atoms prefer positions that are bound to copper. The
optical absorption spectra of these materials have
been investigated. The optical band gap varies as a function of
the sulfur−selenium ratio. Extended Hückel
crystal orbital calculations have been performed to investigate the
electronic structure and bonding in these
compounds in an attempt to explain the site distribution of sulfur and
selenium.