Inorganic Chemistry
Article
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12.30 ([Zn (L1) (OTf) ] ), 798.53 ([Zn (L1) (OTf) ] ),
In the structural refinement of Zn-1, the non-H atoms were refined
anisotropically and the H atoms were fixed geometrically at calculated
distances and allowed to ride on the parent non-H atoms. The highly
disordered state of the incorporated molecule solvents meant that lots
of them could not be located, and hence in the final refinement, the
electron density was treated with the SQUEEZE routine in the
PLATON program package. The Zn center atoms and some of the C
and N atoms in the porphyrin rings and several pyridine rings were
disordered into two parts, with the s.o.f. of each part being refined
using a free variable. To assist in the stability of the refinements,
several restraints were applied: (1) Geometrical constraints of
idealized regular polygons for the disordered pyridine rings in the
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03.91 ([Zn (L1) (OTf) ] ), 1035.40 ([Zn (L1) (OTf) ] ),
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204.60 ([Zn (L1) (OTf) ] ), 1430.02 ([Zn (L1) (OTf) ] ).
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Preparation of Zn-2. A mixture of L2 (87.8 mg, 0.06 mmol) and
zinc bis(trifluoromethane sulfonimide) (50.0 mg, 0.08 mmol) was
suspended in 20 mL of CH CN in a sealed vessel. The reaction
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mixture was heated at 70 °C for 16 h. This solution was added to
diethyl ether, and the product was obtained after centrifugation and
then dried. The desired product was obtained as a purple solid in
5.0% yield (117.1 mg). Anal. Calcd for C560H336N112O F S Zn ·
H O: C, 48.46; H, 2.50; N, 11.30. Found: C, 48.42; H, 2.56; N,
1.24. H NMR (CD CN, 500 MHz): δ 9.59 (24H, s), 9.39 (24H, s),
.99 (48H, s), 8.96 (24H, d, J = 10.0 Hz), 8.92 (24H, d, J = 5.0 Hz),
.76 (24H, d, J = 5 Hz), 8.68 (24H, d, J = 5 Hz), 8.45 (24H, t, J = 5
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88 96 32 14
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ligand and coordinated DMF molecules were used. (2) Lots of atoms
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in the CF
SO
anions were disordered, with the s.o.f. being fixed at
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Hz), 8.33 (48H, d, J = 5 Hz), 8.26 (48H, d, J = 5 Hz), 7.97 (24H, t, J
suitable value. Many of the respective bond distances in the CF SO
3 3
=
5 Hz). 13C NMR (CD CN, 500 MHz): δ 163.24, 150.84, 148.80,
anions and the solvent diethyl ether molecules were restrained to the
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48.15, 142.82, 140.31, 140.31, 138.47, 135.56, 134.47, 132.38,
28.55, 124.40, 124.21, 123.15, 119.38, 116.75. F NMR (CD CN,
00 MHz): δ 80.15. IR (KBr pellet, ν/cm ): 1658 (s), 1602 (m),
527 (s), 1475 (w), 1440 (w), 1402 (w), 1348 (s), 1197 (vs), 1135
idealized geometry. (3) The thermal parameters on adjacent atoms in
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some of the CF
SO
anions were restrained to be similar. The A and
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B alerts in CheckCif were caused by the poor quality of the crystal
resulting in weak diffraction intensities and the presence of disordered
coordinated and free solvent molecules.
(
s), 1054 (s), 997 (m), 904 (w), 856 (w), 798 (w), 758 (w), 738 (w),
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55 (w), 613 (w), 570 (w), 509 (w). ESI-MS: m/z 781.96
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(
(
(
(
[Zn (L2) (NTf ) ] ), 870.45 ([Zn (L2) (NTf ) ] ), 975.12
[Zn (L2) (NTf ) ] ), 1100.33 ([Zn (L2) (NTf ) ] ), 1253.91
[Zn (L2) (NTf ) ] ), 1445.63 ([Zn (L2) (NTf ) ] ), 1692.28
[Zn (L2) (NTf ) ] ).
ASSOCIATED CONTENT
sı Supporting Information
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General Procedure for the Cage-Based Catalysis. To a
solvent mixture of CH CN and DMF [3:1 (v/v), 4 mL] were added
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Measurements and materials, preparation and character-
izations, NMR data, NMR and IR spectra, UV−vis
titrations, and kinetic analysis (PDF)
CH CN stock solutions of NAI (12 mM), PC (18 mM), and biphenyl
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(
5 mM solution) and Zn-1 (21.1 mg, 0.5 mM) or Zn-2 (27.7 mg, 0.5
mM). The mixture solution was stirred at 50 °C for 12 h. At various
times, an aliquot (50 μL) was taken from the solution and added to
diethyl ether (1 mL), which was then passed through a filter
membrane (0.22 mm) to remove the catalyst. The formation of
products was monitored by gas chromatography (GC) relative to an
internal standard (biphenyl). The pure products were obtained using
CCDC 2015811 contains the supplementary crystallographic
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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column chromatography and characterized using H and C NMR.
General Procedure for Examination of the Multiple Turn-
over Catalysis. To a solution of 0.5 mM of each cage in CH CN/
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DMF (3:1 in volume), we added several successive portions of NAI
(
20 mM) and 2-PC (30 mM), stirring each one for 12 h at 50 °C
before adding the next portion.
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Molecular Simulations. DFT-based calculations, with the full-
Corresponding Authors
electron Gaussian-type basis sets developed by Collins and Hehre for
C, N, and H atoms
potentials developed by Hay, Wadt, and co-workers,
conjunction with the B3LYP functional,
Gaussian 16, revision A03, were performed to understand the
mechanisms for the acyl-transfer reactions.
Cheng He − State Key Laboratory of Fine Chemicals, Dalian
Xin Liu − State Key Laboratory of Fine Chemicals, Dalian
48,49
together with Los Alamos effective core
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in
as implemented in
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Host−Guest Chemistry Studied Using UV−Vis Spectrosco-
py. A solution of Zn-1 or Zn-2 in CH CN/DMF (3:1 in volume; 3
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mL, 0.5 or 0.25 μM) was transferred to a cuvette. Small aliquots of the
guest solution were titrated into the cuvette. The experiment was
performed at room temperature. Using nonlinear analysis with the
DynaFit program (Biokin Software), the binding equation derived
for a 1:1 model (noncooperative model) was then fitted to the data
obtained from the UV−vis titration.
Crystallography. The X-ray intensities of the complexes were
collected on a Bruker SMART APEX CCD diffractometer with
graphite-monochromated Mo Kα (λ = 0.71073 Å) using the SMART
Authors
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LiLi Li − State Key Laboratory of Fine Chemicals, Dalian
University of Technology, Dalian 116012, P. R. China
Linlin Yang − Xinxiang Key Laboratory of Forensic Science
Evidence, School of Forensic Medicine, Xinxiang Medical
University, Xinxiang 453003, P. R. China
Xuezhao Li − State Key Laboratory of Fine Chemicals, Dalian
University of Technology, Dalian 116012, P. R. China
Jing Wang − State Key Laboratory of Fine Chemicals, Dalian
University of Technology, Dalian 116012, P. R. China
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and SAINT programs.
methods and refined on F by full-matrix least-squares methods with
SHELXTL-2018.
The structures were solved by direct
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Crystal Data for Zn-1. C4 7 4 H3 9 4 F4 8 N7 8 O6 6 S1 6 Zn1 4
Zn (C H N Zn) ·16CF SO ·6C NOH ·8C H O·4H O], M =
[
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68 44 12
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0578.8, tetragonal, space group P4/n, black block, a = 34.401(5)
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Å, b = 34.401(5) Å, c = 27.321(4) Å, β = 90°, V = 32333(8) Å , Z = 2,
D = 1.087 g cm , μ(Mo Kα) = 0.633 mm , T = 200(2) K, 28190
unique reflections [Rint = 0.0566], final R [with I > 2σ(I)] = 0.0997,
−3
−1
c
Notes
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wR (all data) = 0.2624 for 2θ = 50°, CCDC 2015811.
The authors declare no competing financial interest.
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Inorg. Chem. 2021, 60, 8802−8810