Syntheses and structures of thiophosphorylatocavitands and their reactivity towards first-row transition metal halides

Article abstract of DOI:10.1080/24701556.2020.1749073

Two-step reactions of resorcin[4]arene (1) or methylresorcin[4]arene (2) with PPhCl₂ and subsequent in situ oxidation with sulfur powder afforded a series of new thiophosphorylatocavitands 1a–1d or 2a–2d, respectively. Molecular structures of 1

Full text of DOI:10.1080/24701556.2020.1749073

Inorganic and Nano-Metal Chemistry
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Syntheses and structures of
thiophosphorylatocavitands and their reactivity
towards first-row transition metal halides
Xiao-Li Liu, Jing-Long Liu, Nian-Nian Wang, Ai-Quan Jia & Qian-Feng Zhang
To cite this article: Xiao-Li Liu, Jing-Long Liu, Nian-Nian Wang, Ai-Quan Jia & Qian-Feng
Zhang (2020): Syntheses and structures of thiophosphorylatocavitands and their reactivity
towards first-row transition metal halides, Inorganic and Nano-Metal Chemistry, DOI:
10.1080/24701556.2020.1749073
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INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2020.1749073
Syntheses and structures of thiophosphorylatocavitands and their reactivity
towards first-row transition metal halides
Xiao-Li Liu, Jing-Long Liu, Nian-Nian Wang, Ai-Quan Jia, and Qian-Feng Zhang
Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, Ma’anshan, Anhui, P. R. China
ABSTRACT
ARTICLE HISTORY
Received 15 April 2019
Accepted 10 March 2020
Two-step reactions of resorcin[4]arene (1) or methylresorcin[4]arene (2) with PPhCl2 and subse-
quent in situ oxidation with sulfur powder afforded a series of new thiophosphorylatocavitands
1a–1d or 2a–2d, respectively. Molecular structures of 1aꢀC3H6O, 1dꢀC3H6OꢀCH4O, 2aꢀ2C2H6Oꢀ2H2O,
and 2bꢀ2C4H8O have been determined by X-ray diffraction analysis, which showed the C4v stereo-
isomer with the four P ¼ S bonds oriented towards the molecular cavity. The binding ability of thi-
ophosphorylatocavitands 1a and 2b towards Cu(I), Mn(II), Co(II), Cu(II), and Zn(II) halides was
studied by UV/vis absorption.
KEYWORDS
Resorcin[4]arene; host–
guest; thiophosphorylatoca-
vitand; synthesis;
crystal structure
Introduction
specie by the comparison of Mn(II), Co(II), Cu(II), and
Zn(II) species.
The cavitand structure is obtained by the bridging of a
resorcarene molecule with various moieties, including alkyl
groups (e.g., methylene), aromatic pacers, or phosphorus
and silicon moieties.[1–9] Peculiarly, the studies of phos-
phorus-containing derivatives of resorcinarenes demon-
strated their wide applicability for the complexation and
separation of metal ions.[10–12] Phosphorus-containing
groups play an important role in host–guest chemistry and
the properties of the phosphoryl (P ¼ O) and thiophosphoryl
(P ¼ S) groups have been proved to be particularly good
donors for metal ions.[13–16] It has been reported that the
phosphoryl group binds alkali or alkaline earth metal ions
through its oxygen atom, whereas the sulfur atom of the
P ¼ S thiophosphoryl group has more affinity for soft cati-
ons. Previously, Dutasta reported that the tetra-thiophospho-
natocavitand with long-chain alkyl substituents in its iiii
configuration exhibits excellent extraction properties for soft
metal ions, with a better affinity for Agþ (91%), than for
Tlþ (38%) and Hg2þ (16%). The extraction of other picrate
salts (Cu2þ, Ni2þ, Co2þ, Zn2þ, Cd2þ, Pb2þ) was not
detected.[12,17] The P ¼ S thiophosphoryl group was attached
to the resorcin[4]arene skeleton to produce the thiophos-
phorylated cavitand by using a two-step synthesis in this art-
icle.[17] It was thus interesting to explore the possibilities of
thiophosphorylated cavitands with different substituents to
complex with first-row transition metal species, such as
MnCl2, CoCl2, CuCl2, ZnCl2, CuCl, and CuI, by UV/vis
absorption.[18] We report herein that thiophosphorylated
Experimental section
General considerations
All reactions were carried out under a nitrogen atmosphere,
and solvents were purified, if necessary, by standard proce-
dures prior to use. 2-Methylresorcinol, resorcinol, ethanal,
propanal, n-butanal, iso-butyl aldehyde, n-pentanal, iso-pen-
tyl aldehyde, and dichlorophenylphosphine (97%) were pur-
chased from Alfa Aesar Ltd. and used as received.
Resorcin[4]arene 1 and methylresorcin[4]arene 2 were pre-
pared according to the literature methods.[19] NMR spectra
were recorded on a Bruker ALX 400 Plus spectrometer oper-
ating at 400 and 162 MHz for 1H and 31P, respectively.
Chemical shifts (d, ppm) were reported with reference to
SiMe4 (1H) and H3PO4 (31P). Infrared spectra (KBr) were
recorded on a Perkin-Elmer 16 PC FT-IR spectrophotometer
with use of pressed KBr pellets. UV/vis absorption spectra
were measured on a Purkinje General TU-1901 spectropho-
tometer. To a solution of resorcin[4]arene(O2P(S)Ph)4 or
methylresorcin[4]arene(O2P(S)Ph)4 in acetone (5 mL) was
added 2–4 equiv metal halides and the progress of reaction
was monitored by UV/vis spectroscopy. Elemental analyses
were carried out using a Perkin-Elmer 2400 CHN analyzer.
Synthesis of resorcin[4]arene(O2P(S)Ph)4 (1a)
To a solution of 1 (1.50 g, 2.50 mmol) in 20 mL dry pyridine,
cavitands have better extraction properties towards Cu(I) dichlorophenylphosphine (1.86 g, 10.4 mmol) was added
CONTACT Q.-F. Zhang
ahutchang@yahoo.com; zhangqf@ahut.edu.cn
Institute of Molecular Engineering and Applied Chemistry, Anhui University of
Technology, Ma’anshan, Anhui 243002, P. R. China.
Supplemental data for this article can be accessed at the publisher’s website.
ß 2020 Taylor & Francis Group, LLC

2
X.-L. LIU ET AL.
slowly, at room temperature. After stirring for 4 h at 80 ꢁC, Synthesis of methylresorcin[4]arene(O2P(S)Ph)4 (2a)
S8 (0.33 g, 1.30 mmol) was added and the mixture was
To a solution of 2 (2.18 g, 3.33 mmol) in 35 mL dry pyridine,
stirred again for 3 h. The solvent was removed under vac-
dichlorophenylphosphine (2.41 g, 13.49 mmol) was added
uum and the crude product was washed with water and
slowly at room temperature. After stirring for 4 h at 80 ꢁC,
dried under vacuum. Pure product was obtained as a white
S8 (0.43 g, 1.66 mmol) was added and the mixture was
solid by recrystallization from acetone/water (v:v ¼ 5:1) in
stirred again for 3 h. The solvent was removed under vac-
1
ca. 56% yield (1.62 g). H NMR (CDCl3): d (ppm) 8.19 (dd,
uum and the crude was washed with water and dried under
8H, P(O)ArHo), 7.54 (m, 4H þ 8H, P(O)ArHm þ P(O)ArHp),
vacuum. Pure product was obtained as white solid by recrys-
7.30 (s, 4H, ArHlower), 6.69 (s, 4H, ArHupper), 4.65 (t, 4H,
tallization from tetrahydrofuran/ethanol (v:v ¼ 4:1) in ca.
3J ¼ 3.6 Hz, bridge CH), 2.39 (m, 8H, CH2CH3), 1.06 (t,
1
72% yield (2.90 g). H NMR (CDCl3): d (ppm) 8.21 (dd, 8H,
12H, 3J ¼ 3.4 Hz, CH2CH3); 31P NMR (CDCl3): d (ppm)
P(O)ArHo), 7.59 (m, 4H þ 8H, P(O)ArHm þ P(O)ArHp),
79.49 (s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1432.7,
7.16 (s, 4H, ArCH), 4.95 (t, 4H, 3J ¼ 3.2 Hz, bridge CH),
ꢀP–O ¼ 1051.2, ꢀP¼S ¼ 686.2. Anal. Calc. for C60H52O8P4S4:
2
3.75 (s, 12H, ArCH3), 1.85 (d, 12H, J ¼ 3.2 Hz, CH2CH3);
C 62.49%, H 4.55%; Found: C 62.52%, H 4.58%.
31P NMR (CDCl3) d (ppm): 74.96 (s). Selected IR (KBr,
cmꢂ1): ꢀP–Ph ¼ 1432.7, ꢀP–O ¼ 1088.5, ꢀP¼S ¼ 690.7. Anal.
Calc. for C60H52O8P4S4: C 62.49%, H 4.55%; Found: C
62.46%, H 4.51%.
Synthesis of resorcin[4]arene(O2P(S)Ph)4 (1b)
This was prepared similar to 1a. Pure product was obtained
as a white solid by recrystallization from acetone/water
1
Synthesis of methylresorcin[4]arene(O2P(S)Ph)4 (2b)
(v:v ¼ 4:1). Yield: 2.26 g, 75%. H NMR (CDCl3): d (ppm)
8.16 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H,
P(O)ArHm þ P(O)ArHp), 7.29 (s, 4H, ArHlower), 6.71 (s, 4H,
This was prepared similar to 2a. Pure product was obtained
as white solid by recrystallization from tetrahydrofuran/
2
1
ArHupper), 4.34 (d, 4H, J ¼ 6.0 Hz, bridge CH), 2.97 (m, 4H,
methanol (v:v ¼ 4:1). Yield: 3.75 g, 89%. H NMR (CDCl3): d
2
CH(CH3)2), 1.08 (d, 24H, J ¼ 3.0 Hz, CH(CH3)2); 31P NMR
(ppm) 8.19 (dd, 8H, P(O)ArHo), 7.53 (m, 4H þ 8H,
P(O)ArHm þ P(O)ArHp), 6.25 (s, 4H, ArCH), 4.65 (t, 4H,
(CDCl3): d (ppm) 78.95 (s). Selected IR (KBr, cmꢂ1):
ꢀP–Ph ¼ 1441.0, ꢀP–O ¼ 1059.4, ꢀP¼S ¼ 690.3. Anal. Calc. for
C64H60O8P4S4: C 63.56%, H 5.00%; Found: C 63.59%,
H 5.02%.
3
3J ¼ 3.6 Hz, bridge CH), 2.39 (t, 8H, J ¼ 3.6 Hz, CH2CH3),
3
2.18 (s, 12H, ArCH3), 1.06 (t, 12H, J ¼ 3.4 Hz, CH2CH3);
31P NMR (CDCl3) d (ppm): 75.12 (s). Selected IR (KBr,
cmꢂ1): ꢀP–Ph ¼ 1436.9, ꢀP–O ¼ 1068.1, ꢀP¼S ¼ 686.2. Anal.
Calc. for C64H60O8P4S4: C 63.56%, H 5.00%; Found: C
63.60%, H 5.04%.
Synthesis of resorcin[4]arene(O2P(S)Ph)4 (1c)
This was prepared similar to 1a. Pure product was obtained
as a white solid by recrystallization from acetone/methanol
1
Synthesis of methylresorcin[4]arene(O2P(S)Ph)4 (2c)
(v:v ¼ 5:2). Yield: 2.66 g, 88%. H NMR (CDCl3): d (ppm)
8.15 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H,
P(O)ArHm þ P(O)ArHp), 7.00 (s, 4H, ArHlower), 6.70 (s, 4H,
This was prepared similar to 2a. Pure product was obtained
as white solid by recrystallization from tetrahydrofuran/
3
1
ArHupper), 4.29 (t, 4H, J ¼ 5.8 Hz, bridge CH), 2.92 (m, 8H,
methanol (v:v ¼ 5:2). Yield: 2.36 g, 56%. H NMR (CDCl3): d
CH2CH2CH3), 1.43 (m, 8H, CH2CH2CH3), 1.02 (t, 12H,
3J ¼ 5.0 Hz, CH2CH2CH3); 31P NMR (CDCl3): d (ppm) 78.85
(s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1432.7, ꢀP–O ¼ 1063.6,
ꢀP¼S ¼ 690.3. Anal. Calc. for C64H60O8P4S4: C 63.56%, H
5.00%; Found: C 63.51%, H 4.97%.
(ppm) 8.21 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H,
P(O)ArHm þ P(O)ArHp), 7.13 (s, 4H, ArCH), 4.29 (d, 4H,
2J ¼ 5.6 Hz, bridge CH), 2.95 (m, 4H, CH(CH3)2), 2.15 (s,
12H, ArCH3), 1.05 (s, 24H, CH(CH3)2); 31P NMR (CDCl3):
d (ppm) 74.14(s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1432.7,
ꢀP–O ¼ 1071.9, ꢀP¼S ¼ 686.2. Anal. Calc. for C68H68O8P4S4:
C 64.54%, H 5.42%; Found: C 64.56%, H 5.46%.
Synthesis of resorcin[4]arene(O2P(S)Ph)4 (1d)
This was prepared similar to 1a. Pure product was obtained
Synthesis of methylresorcin[4]arene(O2P(S)Ph)4 (2d)
as a white solid by recrystallization from acetone/methanol
1
(v:v ¼ 5:1). Yield: 2.46 g, 78%. H NMR (CDCl3): d (ppm)
This was prepared similar to 2a. Pure product was obtained
8.15 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H, as white solid by recrystallization from tetrahydrofuran/
1
P(O)ArHm þ P(O)ArHp), 7.29 (s, 4H, ArHlower), 6.66 (s, 4H, methanol (v:v ¼ 5:2). Yield: 3.14 g, 72%. H NMR (CDCl3): d
3
ArHupper), 4.91 (t, 4H, J ¼ 4.2 Hz, bridge CH), 2.23 (m, 8H, (ppm) 8.20 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H,
CH2(CH2)2CH3), 1.64 (m, 16H, CH2(CH2)2CH3), 1.07 (t, P(O)ArHm þ P(O)ArHp), 7.13 (s, 4H, ArCH), 4.73 (t, 4H,
12H, 3J ¼ 3.4 Hz, CH2(CH2)2CH3); 31P NMR (CDCl3): d 3J ¼ 5.4 Hz, bridge CH), 2.29 (m, 8H, CH2CH2CH3), 2.12 (s,
(ppm) 79.62 (s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1441.0, 12H, ArCH3), 1.42 (m, 8H, CH2CH2CH3), 1.04 (t, 12H,
ꢀP–O ¼ 1084.3, ꢀP¼S ¼ 682.0. Anal. Calc. for C68H68O8P4S4: 3J ¼ 3.4 Hz, CH2CH2CH3); 31P NMR (CDCl3): d (ppm)
C 64.54%, H 5.42%; Found: C 64.55%, H 5.44%.
74.86(s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1432.7,

INORGANIC AND NANO-METAL CHEMISTRY
3
Table 1. Crystallographic data for 1aꢀC3H6O, 1dꢀC3H6OꢀCH4O, 2aꢀ2C2H6Oꢀ2H2O, and 2bꢀ2C4H8O.
Compound
1aꢀC3H6O
1dꢀC3H6OꢀCH4O
2aꢀ2C2H6Oꢀ2H2O
2bꢀ2C4H8O
CCDC number
1416618
C63H58O9P4S4
1211.21
293
1416619
C72H78O10P4S4
1355.46
293
1416620
C64H68O12P4S4
1281.30
293
1416621
C72H76O10P4S4
1353.45
293
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
Monoclinic
P2/n
Monoclinic
C2/c
Orthorhombic
Pbcn
Triclinic
P-1
a/Å
b/Å
16.0073(11)
12.0149(8)
17.3420(12)
–
93.246(1)
–
3330.0(4)
2
0.296
29.37(2)
11.974(10)
25.49(2)
–
120.53(6)
–
7721(10)
4
0.257
30.46(2)
16.649(11)
27.971(19)
–
13.181(7)
15.963(8)
16.927(9)
88.079(7)
85.780(7)
89.318(7)
3550(3)
2
0.280
17,836
12,162
0.0518
c/Å
a/ꢁ
b/ꢁ
–
–
c/ꢁ
U/Å3
14187(16)
8
0.274
84,519
15,987
Z
l(Mo Ka)/mm–1
Reflections collected
Independent reflections
Rint
20,274
7626
0.0326
22,990
8872
0.1080
0.1343
Final R1a, wR2b [I > 2r(I)]
[all data]
0.0729, 0.1266
0.0994, 0.1561
1.057
0.0857, 0.2131
0.1118, 0.2776
0.924
0.0978, 0.2411
0.1561, 0.3343
0.946
0.1343, 0.2636
0.1831, 0.2870
1.275
GoFc
aR1 ¼ jjFoj – jFcjj/jFoj.
cGoF ¼ [w(jFoj – jFcj)2/(Nobs – Nparam)]1/2
bwR2 ¼ [w(jFo j – jFc j)2/wjFo j ]
.
2
2
2 2 1/2
.
ꢀP–O ¼ 1063.6, ꢀP¼S ¼ 690.9. Anal. Calc. for C68H68O8P4S4: phosphorus atoms to yield the C4v stereoisomer, the four
C 64.54%, H 5.42%; Found: C 64.52%, H 5.40%.
P ¼ S bonds being oriented towards the molecular cavity.
The stereo-chemistry of hosts 1a–1d and 2a–2d were estab-
1
lished from the H and 31P NMR spectra, which revealed a
X-ray diffraction measurements
C4v molecular symmetry. The solid state structure determin-
ation undoubtedly proved the C4v configuration (Figures
1–4). The formation of the C4v isomer is particularly
important to favor the formation of intra-cavity complexes
with metal halide species.
Crystallographic data and experimental details for
1aꢀC3H6O,
1dꢀC3H6OꢀCH4O,
2aꢀ2C2H6Oꢀ2H2O,
and
2bꢀ2C4H8O are summarized in Table 1. Intensity data were
collected on a Bruker SMART APEX 2000 CCD diffractom-
eter using graphite-monochromated Mo Ka radiation
(k ¼ 0.71073 Å) at 293(2) K. The collected frames were proc-
essed with the software SAINT.[20] The data were corrected
for absorption using the program SADABS.[21] Structures
were solved by the direct methods and refined by full-matrix
least-squares on F2 using the SHELXTL software pack-
age.[22,23] All non-hydrogen atoms except for the lattice solv-
ent molecules were refined anisotropically. The positions of
all hydrogen atoms were generated geometrically
The characteristic bands for the thiophosphorylated cavi-
tands 1a–1d and 2a–2b were found in the ranges of
1433–1441 and 1051–1088 cmꢂ1 in their IR spectra. The for-
mer is assignable to the mode of P–phenyl bonds, and the
latter is due to the P–O bonds. The weak bands at 682–690
may be attributed to the ꢀ(P ¼ S) absorptions.[24,25] The
1
31Pf Hg NMR spectra of the thiophosphorylated cavitands
show a singlet at d ¼ 79.49 ppm for 1a, d ¼ 78.95 ppm for
1 b, d ¼ 78.85 ppm for 1c, d ¼ 79.62 ppm for 1d,
d ¼ 74.96 ppm for 2a, d ¼ 75.12 for 2 b, d ¼ 74.14 ppm for
2c, and d ¼ 74.86 ppm for 2d, revealing a C4v molecular
(Csp3–H ¼ 0.96 and
C
sp2–H ¼ 0.93 Å), assigned isotropic
thermal parameters, and allowed to ride on their respective
parent carbon or nitrogen atoms before the final cycle of symmetry, similar to that in other known thiophosphory-
least-squares refinement. The solvent molecules such as acet- lated cavitands (d ¼ 80.03 ppm).[17] The 31Pf Hg NMR reso-
1
one 1aꢀC3H6O and tetrahydrofuran in 2bꢀ2C4H8O, and etha- nances for the resorcin[4]arene(O2P(S)Ph)4 compounds
nol and water molecules in 2aꢀC2H6OꢀH2O were obviously
downfield
relative
to
those
of
isotropically refined without hydrogen atoms due to heavy methylresorcin[4]arene(O2P(S)Ph)4, such the 31P resonances
disorder, which probably resulted in the relatively high R shift upfield possible due to a litter strong coupling effects
values in the final refinement.
between phosphorous atoms and protons of phenyl rings in
resorcin[4]arene(O2P(S)Ph)4 compounds relative to those
between phosphorous atoms and the methyl moieties of
phenyl rings in methylresorcin[4]arene(O2P(S)Ph)4 com-
Results and discussion
1
pounds. The similar absorption peaks of the 31Pf Hg NMR
The phosphorylations of resorcinarenes 1 and 2 by ca.
4 equiv of dichlorophenylphosphine were performed in dry
pyridine at 80 ꢁC. Thiophosphatocavitands were obtained by
spectra for thiophosphorylated cavitands 1a–1d are
observed, indicating that different substituted alkyl frag-
subsequent in situ oxidation of the parent phosphine com- ments of the thiophosphorylated cavitands have little influ-
pounds with sulfur powder (Scheme 1). This reaction pro- ence on the phosphorous chemical shielding due to the
ceeded with the same stereo-selectivity on the four weak remoteness effect.

4
X.-L. LIU ET AL.
Scheme 1. Reactions of resorcinarenes 1 or 2 with dichlorophenylphosphine and the thiophosphatocavitands further oxidized by sulfur. Reagents and conditions:
(i) Resorcin[4]arene/methylresorcin[4]arene, PPhCl2, dry pyridine, 80 ꢁC; (ii) sulfur, dry pyridine, 80 ꢁC.
Structures of the free thiophosphorylated cavitands 1a, 4.331(1) Å], to form a claw-like square conformation. The
1d, 2a, and 2b have been established by X-ray crystallog- structure of 1d, similar to that of 1a, is shown in Figure 2.
raphy. The molecular structure of 1a is shown in Figure The average P ¼ S bond length of 1.898(1) Å is slightly
1(a). Complex 1a crystallizes in the monoclinic space group shorter than that in 1a. The P–phenyl groups with the least
P2/n with one molecule of the thiophosphorylated cavitand observed torsion angle [108.04(2)ꢁ for S1–P1–C23–C24] and
and one acetone solvent molecule entrapped in a cavity of the largest observed torsion angle [159.22(2)ꢁ for
the unit cell, shown in Figure 1(b). The molecule adopts C4v S2–P2–C29–C34] are in different orientation. The iso-butyl
bowl-shaped conformation with four P ¼ S bonds oriented fragments in 1d connected to the bridging carbon atoms act
towards the molecular cavity. The four aromatic cycles like a four-legged piano stool. In 1a, the ethyl fragments are
defining the cavity have about the same angle of inclination attached to the four bridging carbon atoms.
to the plane perpendicular to the C4 axis of the molecule
Methylresorcin[4]arene 2, compared with resorcin[4]
(56.3ꢁ 0.7). The neighboring aromatic cycles of the cavity arene 1, contains four methyl groups at the benzene rings.
are at the same angle relative to the phenyl plane (ca. 33.7ꢁ) Thus, in compounds 2a–2d, the four methyl groups appear
to insure the bowl-shaped conformation. The apical P ¼ S in the apical positions and deepen the cavity and undergo
fragments are combined at the upper rim with the bond the C–Hꢀꢀꢀp interactions. The molecular structures of 2a and
lengths (1.906(1) Å for P1 ¼ S1 and 1.905(1) Å for P2 ¼ S2). 2b are illustrated in Figures 3 and 4, respectively. The four
The P ¼ S bonds and the phenyl substituents are in the axial aromatic rings define the cavity of 2a with different angles
and equatorial positions, respectively. The four fused eight of inclination to the plane perpendicular to the C4 axis of
membered-rings adopt a bowl-shaped conformation to the molecule (the largest angle is 56.70(6)ꢁ and the smallest
entrap an acetone molecule in the center of the cavity. The angle is 53.72(8)ꢁ). The adjacent sulfur atoms in the mol-
P–phenyl groups are in different orientations towards the ecule of 2a, with different separations [S1ꢀꢀꢀS2, 4.641(2);
adjacent P ¼ S bonds; the least observed torsion angle is S2ꢀꢀꢀS3, 4.376(2); S3ꢀꢀꢀS4, 4.634(2); S4ꢀꢀꢀS1, 4.427(2) Å], form
59.66(2)ꢁ for S2–P2–C25–C30 and the largest one is a distorted square. The P ¼ S bonds at the upper rim also
68.24(2)ꢁ for S1–P1–C19–C24. The adjacent sulfur atoms adopt the orientation towards the molecular cavity, similar
are equal distant in para-positions [4.051(1) Å and to 1a and 1d, which can act as the polydentate ligands for

INORGANIC AND NANO-METAL CHEMISTRY
5
Figure 3. Molecular structure of 2a.
Figure 1. (a) Molecular structure of 1a. (b) Molecular view of the acetone guest
at the base of 1a.
Figure 4. Molecular structure of 2b.
the formation of coordination compounds. Complex 2b
crystallizes in the orthorhombic space group Pbcn with one
molecule of cavitand and two THF molecules in the unit
cell. The mean angle of inclination of the four aromatic
rings with the plane perpendicular to the C4 axis of the mol-
ecule was 55.30(2)ꢁ (the largest angle is 57.92(2)ꢁ and the
smallest angle is 52.48(2)ꢁ). The four sulfur atoms in mol-
ecule of 2b form a distorted square with different separa-
tions [S1ꢀꢀꢀS2, 4.153(2); S2ꢀꢀꢀS3, 4.509(2); S3ꢀꢀꢀS4, 4.088(2);
S4ꢀꢀꢀS1, 4.681(2) Å], providing a clawed coordination site.
The cavitands can be used to extract metal halide species
from solutions. The reactivity of the thiophosphorylatocavi-
tands 1a and 2b towards the first-row transition metal hal-
ide species was studied by UV/vis absorption. The pure
Figure 2. Molecular structure of 1d.

6
X.-L. LIU ET AL.
transition metal halide species was studied by the UV/vis
spectroscopy. It has been shown that thiophosphorylatocavi-
tands show special binding ability towards the Cu(I) specie.
Following these observations, we are now continuing our
studies of the combination of other transition metal species
such as silver(I) and gold(I) with thiophosphorylated
cavitands.[12]
Funding
This project was supported by the Natural Science Foundation of
China [90922008].
References
Figure 5. UV/vis absorption of 1a towards CuCl, CuI, MnCl2, CoCl2, CuCl2, and
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