Inorganic Chemistry
Article
luminescent and a precursor to forming {Cu } in a rapid
the experiment was carried out in acetone solvent (100 mL). Yellow
crystals of (2) suitable for X-ray diffraction analysis were obtained by
96
fashion through simple recrystallization, and this is subject to
further investigation. The new Cu L cluster is highly
diffusion of hexane into acetone solution within a week. Yield 0.99 g
96
96
1
(
(
(
85%). Mp. 138−140 °C. H NMR (300 MHz, d -(CD ) CO): 1.28
6
3 2
emissive in the solid state. The formation of large clusters
with supramolecular wheel structures derived from the
dynamic solvation of smaller cluster units spells out a new
strategy for the design of stable clusters with multifunctionality
and with potential gas storage applications.
d, 576H, CH ), 4.95 (m, 96H, CH) ppm; FTIR data in KBr pellet
cm ): 677, 808, 840, 911, 1088, 1175, 1332, 1373, 1466, 1618,
3
−1
1
702, 2879, 2936, 2979, 3387; Anal. Calcd (%) for
C384H672O192S Cu : C, 26.29; H, 3.86; S, 17.55. Found: C, 26.39;
96
96
H, 3.83; S, 17.38.
Synthesis of [Cu{SC(O)OCH(CH ) }] (2) via a Solventless Route
3
2 96
4
. EXPERIMENTAL SECTION
and Recrystallization in Acetone. Solid potassium O-isopropylmo-
nothiocarbonate (100 mg, 0.632 mmol) was added to [Cu-
4.1. Materials and Instrumentation. Hexafluorophosphoric
(
CH CN) ]PF (236 mg, 0.632 mmol) (molar ratio 1:1) in a clean
3 4 6
acid, KOH, and Cu O were purchased from Sigma-Aldrich and used
2
dry mortar, and the solids were gently mixed. The reactants were
ground together with a pestle for about 2−3 min until a homogeneous
yellow paste formed. The paste is caused by the release of the free
acetonitrile (liquid) and has a distinctive smell. The yellow paste was
left in the mortar in a low heat oven (<50 °C) overnight to evaporate
without further purification. Acetone, acetonitrile, chloroform, and
diethyl ether were purchased from Honeywell. Hexane was purchased
from ACE Chemicals. Propan-2-ol was purchased from Merck.
[
(
Cu(CH CN) ]PF , carbonyl sulfide gas, and K[SC(O)OCH-
CH ) ] ligand were prepared using slight modifications of literature
3 4 6
3
2
52−54
the CH CN off and allow the paste to dry. The resulting yellow solid
3
methods.
was dissolved in acetone (10 mL), filtered over a plug of Celite to
Solvents were purified following standard protocols. All reactions
remove KPF salt, and concentrated under reduced pressure. The
6
were performed in oven-dried Schlenk glassware using standard inert
atmosphere techniques. All reactions were carried out under a N
atmosphere by using standard Schlenk techniques. H NMR spectra
light-yellow solid was recrystallized from acetone, and subsequent
characterization of the material, including a single-crystal X-ray study,
revealed it was identical to the solution formation of [Cu{SC(O)-
OCH(CH ) }] (2).
2
1
were recorded on a Bruker Advance DPX300 FT-NMR spectrometer
operating at 300 MHz, and the chemical shifts (δ) are reported in
ppm. FTIR spectra were recorded on a PerkinElmer spectropho-
tometer with samples prepared as KBr pellets. Melting points were
measured by using a Fargo MP-2D melting point apparatus. The
elemental analyses were performed using a PerkinElmer 2400 CHN
analyzer. Emission spectra were recorded using a Cary Eclipse B10
fluorescence spectrophotometer.
3
2
96
4
.3. Crystallography. Reflections were collected on a Bruker
APEXII CCD diffractometer using graphite monochromated Mo Kα
radiation (λ = 0.71073 Å). Crystals were mounted on the tip of glass
fibers with epoxy resin. Data reduction was performed with SAINT-
55
Plus. Absorption corrections for the area detector were performed
56
by using the SADABS program. Structures were solved by direct
2
methods and refined by full-matrix least-squares methods on F by
4.2. Synthesis. Synthesis of K[SC(O)OCH(CH ) ]. A mixture of 2-
3 2
57
using the SHELXL package incorporated in SHELXTL/PC V6.14
propanol (35 mL, excess) and finely powdered KOH (18.35 g, 0.328
mol) was stirred at 40 °C for 1 h. After cooling the solution to
ambient temperature, 5 mL of deionized H O was added to dissolve
remaining solids. COS gas was generated in a separate flask using a
method adapted from that described by Demselben. Briefly, a stock
57,58
59
software
in OLEX2. The data collections for crystals of 1 and 2
were performed at 150(2) and 298(2) K, respectively. Non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were constrained
in geometrical positions to their parent atoms. The disordered
solvated atoms located at the packing cavities of 1 and 2 were treated
as a diffuse contribution to the overall scattering without specific
atoms position by SQUEEZE/PLATON. Illustrations of some crystal
2
5
4
solution of 55% (w/w) H SO was prepared using 98% H SO and
2
4
2
4
deionized water. To generate an excess of COS (g), 142.66 g (0.4
mol) of this stock solution was added to KSCN (38.87 g, 0.4 mol)
and the mixture was heated to 40 °C. The COS (g) formed was
60
structures were generated in Mercury using POV-Ray. Crystallo-
graphic data of 1 and 2 are listed in Table S1.
directed to the 2-propanol/H O solution of potassium isopropoxide
2
using a cannula. After stirring at ambient temperature for 2 h, 200 mL
of n-hexane was added to the reaction flask and the mixture stirred in
an ice bath for 1 h. The salt was isolated as a white solid by vacuum
filtration and washed with 25 mL of hexane and 10 mL of diethyl
ether before drying in vacuo (10.69 g, 0.0688 mol, 21% yield − based
ASSOCIATED CONTENT
sı Supporting Information
■
*
1
on KOH). H NMR (400 MHz, D O) δ (ppm) 1.14 (d, CH , 6H),
2
3
1
3
4
7
.77 (q, O-CH-C, 1H). C NMR (400 MHz, D O) δ (ppm) 185.02,
2
1
Details regarding instrumentation and characterization;
including UV−vis, ESI-MS, NMR, and X-ray crystallog-
−
0.33, 21.18. FTIR: (cm ) 1585 (CO), 1127 (C−O), 1073 (C−
S).
Solution Synthesis of [Cu{SC(O)OCH(CH ) }] ·2THF (1). To a 250
3
2 16
mL round-bottom flask were added [Cu(CH CN) ](PF ) (0.235 g,
.63 mmol) and K[SC(O)O Pr] (0.100 g, 0.63 mmol) in a 100 mL
3
4
6
i
0
THF solution. The reaction mixture was stirred at room temperature
for 1 h. After 1 h, the reaction mixture was evaporated to dryness
under vacuum. The crude yellow powder was washed thoroughly with
deionized water (20 mL × 5) and extracted with CH Cl (10 mL ×
contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
2
2
5
). The resulting CH Cl extract on evaporation yielded a pale yellow
2 2
powder. Yellow crystals of (1) were obtained by diffusion of hexane
into THF solution after 10 days. Yield 0.97 g (80%). Mp. 120−122
1
°
C. H NMR (300 MHz, d -(CD ) CO): 1.28 (d,96H, CH ), 1.78
6
3
2
3
(
br, 8H, CH ), 3.61 (br, 8H, CH ) 4.94 (br, 16H, CH) ppm; FTIR
2
2
−1
data in KBr pellet (cm ): 681, 841, 911, 1088, 1179, 1332, 1373,
466, 1614, 1702, 2880, 2937, 2980, 3475; Anal. Calcd (%) for
C H O S Cu : C, 28.19; H, 4.21; S, 16.72. Found: C, 28.12; H,
■
1
Corresponding Authors
72
128 34 16
16
Werner E. van Zyl − School of Chemistry and Physics,
3
.89; S, 16.97.
Solution Synthesis of [Cu{SC(O)OCH(CH ) }] (2). The synthetic
3
2 96
procedure and stoichiometric amounts of reactants used for 2 are
similar to those of 1. The only modification in the procedure was that
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Inorg. Chem. 2021, 60, 8973−8983