5 research outputs found
Tris(3,5-di-<i>tert</i>-butylcatecholato)molybdenum(VI): Lewis Acidity and Nonclassical Oxygen Atom Transfer Reactions
In
the solid state, trisÂ(3,5-di-<i>tert</i>-butylcatecholato)ÂmolybdenumÂ(VI)
forms a dimer with seven-coordinate molybdenum and bridging catecholates.
NMR spectroscopy indicates that the dimeric structure is retained
in solution. The molybdenum center has a high affinity for Lewis bases
such as pyridine or pyridine-<i>N</i>-oxide, forming seven-coordinate
monomers with a capped octahedral geometry, as illustrated by the
solid-state structure of (3,5-<sup><i>t</i></sup>Bu<sub>2</sub>Cat)<sub>3</sub>MoÂ(py). Structural data indicate that the
complexes are best considered as MoÂ(VI) with substantial Ï€ donation
from the nonbridging catecholates to molybdenum. Both the dimeric
and the monomeric trisÂ(catecholates) react rapidly with water to form
free catechol and oxomolybdenum bisÂ(catecholate) complexes. Monooxomolybdenum
complexes are also obtained, more slowly, on reaction with dioxygen,
with organic products consisting mostly of 3,5-di-<i>tert</i>-butyl-1,2-benzoquinone with minor amounts of the extradiol oxidation
product 4,6-di-<i>tert</i>-butyl-1-oxacyclohepta-4,6-diene-2,3-dione.
The pyridine-<i>N</i>-oxide complex reacts on heating (with
excess pyO) to form initially (3,5-<sup><i>t</i></sup>Bu<sub>2</sub>Cat)<sub>2</sub>MoOÂ(Opy) and ultimately MoO<sub>3</sub>(Opy),
with quinone and free pyridine as the only organic products. The decay
of (3,5-<sup><i>t</i></sup>Bu<sub>2</sub>Cat)<sub>3</sub>MoÂ(Opy) shows an accelerated, autocatalytic profile because the oxidation
of its product, (3,5-<sup><i>t</i></sup>Bu<sub>2</sub>Cat)<sub>2</sub>MoOÂ(Opy), produces an oxo-rich, catecholate-poor intermediate
which rapidly conproportionates with (3,5-<sup><i>t</i></sup>Bu<sub>2</sub>Cat)<sub>3</sub>MoÂ(Opy), providing an additional pathway
for its conversion to the mono-oxo product. The trisÂ(catecholate)
fragment MoÂ(3,5-<sup><i>t</i></sup>Bu<sub>2</sub>Cat)<sub>3</sub> deoxygenates Opy in this nonclassical oxygen atom transfer
reaction slightly less rapidly than does its oxidized product, MoOÂ(3,5-<sup><i>t</i></sup>Bu<sub>2</sub>Cat)<sub>2</sub>
A Rutile Chevron Modulation in Delafossite-Like Ga<sub>3–<i>x</i></sub>In<sub>3</sub>Ti<sub><i>x</i></sub>O<sub>9+<i>x</i>/2</sub>
The structure solution
of the modulated, delafossite-related, orthorhombic Ga<sub>3–<i>x</i></sub>In<sub>3</sub>Ti<sub><i>x</i></sub>O<sub>9+<i>x</i>/2</sub> for <i>x</i> = 1.5 is reported
here in conjunction with a model describing the modulation as a function
of <i>x</i> for the entire system. Previously reported structures
in the related A<sub>3–<i>x</i></sub>In<sub>3</sub>Ti<sub><i>x</i></sub>O<sub>9+<i>x</i>/2</sub> (A = Al, Cr, or Fe) systems use X-ray diffraction to determine that
the anion lattice is the source of modulation. Neutron diffraction,
with its enhanced sensitivity to light atoms, offers a route to solving
the modulation and is used here, in combination with precession electron
diffraction tomography (PEDT), to solve the structure of Ga<sub>1.5</sub>In<sub>3</sub>Ti<sub>1.5</sub>O<sub>9.75</sub>. We construct a model
that describes the anion modulation through the formation of rutile
chevrons as a function of <i>x</i>. This model accommodates
the orthorhombic phase (1.5 ≤ <i>x</i> ≤ 2.1)
in the Ga<sub>3–<i>x</i></sub>In<sub>3</sub>Ti<sub><i>x</i></sub>O<sub>9+<i>x</i>/2</sub> system,
which transitions to a biphasic mixture (2.2 ≤ <i>x</i> ≤ 2.3) with a monoclinic, delafossite-related phase (2.4
≤ <i>x</i> ≤ 2.5). The optical band gaps of
this system are determined, and are stable at ∼3.4 eV before
a ∼0.4 eV decrease between <i>x</i> = 1.9 and 2.0.
After this decrease, stability resumes at ∼3.0 eV. Resistance
to oxidation and reduction is also presented
Structural, Electrical, and Optical Properties of the Tetragonal, Fluorite-Related Zn<sub>0.456</sub>In<sub>1.084</sub>Ge<sub>0.460</sub>O<sub>3</sub>
We report the discovery of Zn<sub>0.456</sub>In<sub>1.084</sub>ÂGe<sub>0.460</sub>O<sub>3</sub>, a material closely related
to bixbyite. In contrast, however, the oxygen atoms in this new phase
occupy 4 Wyckoff positions, which result in 4 four-coordinate, 24
six-coordinate (2 different Wyckoff positions), and 4 eight-coordinate
sites as compared to the 32 six-coordinate (also 2 different Wyckoff
positions) sites of bixbyite. This highly ordered material is related
to fluorite, Ag<sub>6</sub>GeSO<sub>8</sub>, and γ-UO<sub>3</sub> and is n-type with a bulk carrier concentration of 4.772 ×
10<sup>14</sup> cm<sup>–3</sup>. The reduced form displays
an average room temperature conductivity of 99(11) S·cm<sup>–1</sup> and an average optical band gap of 2.88(1) eV. These properties
are comparable to those of In<sub>2</sub>O<sub>3</sub>, which is the
host material for the current leading transparent conducting oxides.
The structure of Zn<sub>0.456</sub>In<sub>1.084</sub>ÂGe<sub>0.460</sub>O<sub>3</sub> is solved from a combined refinement of
synchrotron X-ray powder diffraction and time-of-flight neutron powder
diffraction and confirmed with electron diffraction. The solution
is a new, layered, tetragonal structure in the <i>I</i>4<sub>1</sub>/<i>amd</i> space group with <i>a</i> =
7.033986(19) Ã… and <i>c</i> = 19.74961(8) Ã…. The
complex cationic topological network adopted by Zn<sub>0.456</sub>In<sub>1.084</sub>ÂGe<sub>0.460</sub>O<sub>3</sub> offers the
potential for future studies to further understand carrier generation
in ∼3 eV oxide semiconductors
Site Dependency of the High Conductivity of Ga<sub>2</sub>In<sub>6</sub>Sn<sub>2</sub>O<sub>16</sub>: The Role of the 7‑Coordinate Site
The 6-coordinated cation site is
the fundamental building block
of the most effective transparent conducting oxides. Ga<sub>2</sub>In<sub>6</sub>Sn<sub>2</sub>O<sub>16</sub>, however, maintains 4-,
6-, 7-, and 8-coordinated cation sites and still exhibits desirable
transparency and high conductivity. To investigate the potential impact
of these alternative sites, we partially replace the Sn in Ga<sub>2</sub>In<sub>6</sub>Sn<sub>2</sub>O<sub>16</sub> with Ti, Zr, or
Hf and use a combined approach of density functional theory-based
calculations, X-ray diffraction, and neutron diffraction to establish
that the substitution occurs preferentially on the 7-coordinate site.
In contrast to Sn, the empty d orbitals of Ti, Zr, and Hf promote
spd covalency with the surrounding oxygen, which decreases the conductivity.
Pairing the substitutional site preference with the magnitude of this
decrease demonstrates that the 7-coordinate site is the major contributor
to conductivity. The optical band gaps, in contrast, are shown to
be site-independent and composition-dependent. After all 7-coordinate
Sn has been replaced, the continued substitution of Sn results in
the formation of a 7-coordinate In antisite or replacement of 6-coordinate
Sn, depending on the identity of the d<sup>0</sup> substitute
Selective Crystal Growth and Structural, Optical, and Electronic Studies of Mn<sub>3</sub>Ta<sub>2</sub>O<sub>8</sub>
Mn<sub>3</sub>Ta<sub>2</sub>O<sub>8</sub>, a stable targeted material with
an unusual and complex cation topology in the complicated Mn–Ta–O
phase space, has been grown as a ≈3-cm-long single crystal
via the optical floating-zone technique. Single-crystal absorbance
studies determine the band gap as 1.89 eV, which agrees with the value
obtained from density functional theory electronic-band-structure
calculations. The valence band consists of the hybridized Mn d–O
p states, whereas the bottom of the conduction band is formed by the
Ta d states. Furthermore, out of the three crystallographically distinct
Mn atoms that are four-, seven-, or eight-coordinate, only the former
two contribute their states near the top of the valence band and hence
govern the electronic transitions across the band gap