2+ Unit-Encapsulated Trimetallic Cages: One-Pot Syntheses and Modulation of Argentophilic Interactions by the Uncoordinated Substituents

Article abstract of DOI:10.1021/acs.inorgchem.8b03388

Four [Ag-Ag]²⁺ unit-encapsulated trimetallic cages 1-4 were synthesized from one new tripodal ligand L and silver salts in different solvent systems by a one-pot method. The formation of coordination cages occurred simultaneously with the condensation of amino groups and ketone. The remarkable structural feature of cages 1-4 is their spontaneous incorporation of [Ag-Ag]²⁺ cationic units. Moreover, the argentophilic interactions are modulated by the uncoordinated amino substituents. The study herein shows that modification and subtle changes of the cage structures could be realized by a one-pot synthetic method.

Full text of DOI:10.1021/acs.inorgchem.8b03388

Communication
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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
[Ag−Ag]2+ Unit-Encapsulated Trimetallic Cages: One-Pot Syntheses
and Modulation of Argentophilic Interactions by the Uncoordinated
Substituents
Guo-Xia Jin,†,‡ Gui-Ying Zhu,†,‡ Yan-Yan Sun,§ Qing-Xiu Shi,† Li-Ping Liang,† Hai-Ying Wang,⊥
Xiang-Wen Wu,† and Jian-Ping Ma*,†
†College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for
Chemical Imaging, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan
250014, People’s Republic of China
⊥College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610066, People’s Republic of China
§QiLu Pharmaceutical (HaiNan) Company, Ltd., Haikou, Hainan 570314, People’s Republic of China
S
* Supporting Information
interesting structural features of the four cages are the
ABSTRACT: Four [Ag−Ag]2+ unit-encapsulated trime-
tallic cages 1−4 were synthesized from one new tripodal
ligand L and silver salts in different solvent systems by a
one-pot method. The formation of coordination cages
occurred simultaneously with the condensation of amino
groups and ketone. The remarkable structural feature of
cages 1−4 is their spontaneous incorporation of [Ag−
Ag]2+ cationic units. Moreover, the argentophilic inter-
actions are modulated by the uncoordinated amino
substituents. The study herein shows that modification
and subtle changes of the cage structures could be realized
by a one-pot synthetic method.
incorporation of [Ag−Ag]2+ cationic units in their cavities and
the modulation of argentophilic interactions by modification of
ligand L. The luminescent properties are also preliminarily
investigated.
The new tripodal ligand L (1H NMR; Figure S1) was
rationally designed and synthesized from 1,3,5-tris-
(bromomethyl)-2,4,6-trimethylbenzene and 4-amino-3-(2-pyr-
idyl)-5-mercapto-1,2,4-triazole. Three semirigid arms afford
both N,N-chelating sites and additional N-binding sites. The
−NH2 pendent groups are easily derivatized through a
condensation reaction, and so that would affect the solubility
and configuration of the ligand. By careful layering of the ethanol
solution of silver salt onto the solution of ligand in 1,4-dioxane in
a 3:2 ratio at room temperature, the cage [Ag5(L)2(SbF6)5]·
3C4H8O2 (1) was obtained in 57% yield (Scheme 1), which was
characterized by 1H NMR (Figure S2), IR, and single-crystal X-
ray diffraction (Figure S6 and Table S1).
he chemistry of supramolecular coordination cages has
T
attracted much attention not only because of their
aesthetic structures but also because of their interesting
properties and possible applications, such as ion and molecular
recognition,1,2 ion exchange,3 selective guest inclusion,4−6
tunable luminescence,7 and catalysis for specific reactions8,9 in
their cavities. Over the past 2 decades, a number of discrete
cagelike molecules MxLy (x and y are positive integers) have
been synthesized by the assembly of organic ligands with
transition metals10−18 and rare-earth elements.6,19−21 For
example, the Stang,13 Fujita,22 Hong,23 and Raymond24,25
groups have made great contributions in this field. Among them,
the M3L2-type coordination cage, as one of the simplest three-
dimensional (3D) cage structures (M3L2 or M2L3), is still rather
uncommon in comparison with various high-symmetry
polyhedra. Although some such supramolecular complexes
have appeared in the literature,3,26−34 the M3L2 molecular cages
that encapsulate metal cations have never been described, to our
knowledge. As we know, the vast majority of reported cagelike
complexes incorporated neutral guest molecules or anions in
their central cavities. Only seldom examples of cages that
encapsulated cations have been reported.7,35,36 Here we report
the construction of four Ag3L2 cagelike complexes from a new
designed tripodal ligand, 1,3,5-tris(4-amino-5-pyridin-2-yl-
1,2,4-triazol-3-ylmercaptomethyl)-2,4,6-trimethylbenzene (L),
and tetrahedral silver(I) centers in different solvent systems. The
As shown in Figure 1, the [Ag3L2]3+ cage motif in 1 consists of
three silver(I) ions and two L ligands. The two ligands have a
cis,cis,cis conformation and a face-to-face orientation; the six
arms of the two ligands are joined together by three silver(I) ions
to give an individual 3D M3L2-type cage, where three lateral
arms are twisted into a triple helix. Each silver center is four-
coordinate with four chelating nitrogen atoms of triazole and
pyridine from two different ligands. The coordination geometry
of the three silver centers is seriously distorted tetrahedral, with
coordination angles ranging from 68.3(7) to 153.4(3)°. The
Ag−N bond lengths fall in the range of 2.237(16)−2.395(9) Å.
The average tetrahedral AgI···AgI separation in 1 is 6.36 Å. The
triazole and pyridine rings that chelate Ag+ ions are close to
coplanar, with the dihedral angles being 1.07−4.26°. The two
benzene ring planes are nearly parallel with each other (the
dihedral angle is 1.07°), and the separation between the two
benzene rings is 9.41 Å. The remarkable structural feature of the
cylinder-like complex 1 is its spontaneous encapsulation of the
cationic [Ag−Ag]2+ unit, as illustrated in Figure 1. The dimer
Received: December 5, 2018
© XXXX American Chemical Society
A
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pot synthetic method by introducing liquid ketone to the
reaction systems. Fortunately, three new cages,
[Ag5(L1)2(BF4)5]·2C3H6O·5CHCl3 (2), [Ag5(L1)2(ClO4)5]·
2C3H6O·5CHCl3 (3), and [Ag5(L2)2(ClO4)5]·C4H8O2·solvent
(4), were obtained in 64%, 52%, and 79% yield, respectively,
which were clearly evidenced by 1H NMR (Figures S3−S5) and
Scheme 1. Synthetic Route of Cages 1−4
1
single-crystal X-ray diffraction (Figures S8−S10). H NMR
spectra indicated that ligand L was converted to L1 (2 and 3)
and L2 (4) in situ in the one-pot assembly processes, by the
absence of −NH2 protons and the presence of methyl and
cyclohexyl protons. Structural analysis showed that 2−4 took on
the same [M3L2]3+ cage motif as 1 and identically encapsulated
cationic [Ag−Ag]2+ units in their cavities, except for variation of
the ligands. The corresponding bond lengths and angles around
the silver(I) ions are listed in Table S2. Further insight into the
structures revealed that the included Ag−Ag distances were 3.34
Å (2), 3.33 Å (3) and 3.12 Å (4), respectively, which were
shortened with the increasing bulk of the amino (1), propan-2-
ylideneamino (2 and 3), and cyclohexylideneamino (4) pendent
groups. Namely, the argentophilic interactions are modulated by
the uncoordinated amino substituents. The weak Ag···π
interactions also exist in complexes 2−4 (Ag···Cg = 3.2 Å,
where Cg = benzene ring centroid). The two benzene ring
planes are also nearly parallel with each other (the dihedral
angles ranging from 1.05 to 4.12°), and the separations between
the two benzene rings are 9.63 Å (2 and 3) and 9.55 Å (4). The
average tetrahedral AgI···AgI separation in 2−4 is 6.55, 6.58, and
6.69 Å, respectively. Most of the triazole and pyridine rings that
chelate tetrahedral Ag+ ions in 2−4 deviate much from coplanar,
with the dihedral angles being 3.79−21.35°.
When ligand L reacted with silver salts in different solvent
systems containing liquid ketone, the formation of [Ag3L2]3+
coordination cages occurred simultaneously with the con-
densation of all six amino groups and ketone. This study
indicated that the condensation of amino groups with ketone
was promoted by the binding of ligand L to silver(I) ions.
Moreover, the Ag−Ag distances of the encapsulated [Ag−Ag]2+
units were affected by modifying the outer environments of the
cages through the choice of ketones with different config-
urations. This result demonstrates that we can modulate the
structures of the cage complexes by a one-pot method.
To investigate the effect of the Ag−Ag distances on the
photoluminescent properties of the cage complexes, the
emissions of 1−4 and ligands L, L1, and L2 were investigated
at room temperature in the solid state (Figure 2). The free ligand
L shows an emission maximum at 480 nm with a shoulder at 445
nm upon excitation at 400 nm, while ligands L1 and L2 show
emission maxima at 490 and 503 nm upon excitation at 390 and
410 nm, respectively, red shifts of 10 and 23 nm compared to L.
When excited at 380 nm, complexes 1−4 produce emission
maxima at 466, 480, 470, and 475 nm, respectively, with the
same shoulders at 445 nm. Compared to ligands L, L1, and L2,
the four complexes 1−4 show similar emission bands except that
the emission maximum blue-shifts by 14, 10, 20, and 28 nm,
respectively. The resemblance in the band shapes indicates that
the emission of complexes 1−4 may be ascribed to a ligand-
centered π−π* or n−π* transition.38 The imination of L leads to
red shifts of the emission peaks in L1 and L2. The blue shifts of
the emission peaks in complexes are probably attributable to the
coordination of ligands to silver(I) ions. On the other hand, the
Ag−Ag interactions might also have an important effect on the
highest occupied molecular orbital (HOMO)−lowest unoccu-
pied molecular orbital (LUMO) energy gap of the complexes,
Figure 1. Crystal structures of the cage complexes 1−4 with stick
diagrams presenting the cages and ball diagrams presenting the [Ag−
Ag]2+ dimers: side view (top) and view along the axis of the cylinder
(bottom). Hydrogen atoms, anions and solvent molecules are omitted
for clarity. Ag: pink, C: dark gray, N: dark blue, S: yellow.
[Ag−Ag]2+ is encapsulated within the cavity of the [Ag3L2]3+
coordination cage by complexation of two trigonal silver(I) ions
with six triazole nitrogen atoms from the two ligands. The bond
angles of ∠N−Ag−N are in the range of 118.5(3)−122.7(4)°,
and the bond distances of Ag−N are 2.204(9)−2.213(9) Å. Five
−
ClO4 anions are located outside the cage. To the best of our
knowledge, the example of cationic cages with cations included
in their cavities is very rare because of the electrostatic repulsive
interactions, and here it seems that the triazole bases and weak
Ag···π interactions (Ag···Cg = 3.0 Å, where Cg = benzene ring
centroid) are responsible for maintaining the [Ag−Ag]2+ unit in
the cationic [Ag3L2]3+ cage (Figure S7). The included Ag−Ag
distance is 3.39 Å, slightly shorter than twice the van der Waals
radius of the silver(I) ion (3.44 Å), suggesting the presence of
significant argentophilic interactions.37
On the basis of the above experimental results, we expected
that the Ag−Ag distance of the encapsulated [Ag−Ag]2+ unit
would be affected by modifying ligand L. We tried to convert
ligand L to L1 and L2 through a condensation reaction with
acetone and cyclohexanone before coordination assembly.
However, the attempt failed, and only two of the three amino
groups were converted into imines. Then we attempted a one-
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Figure 4. Photoluminescent spectra of L, L1, L2, and 1−4 measured at
room temperature in the solution state (in dimethyl sulfoxide).
Figure 2. Photoluminescent spectra of L, L1, L2, and 1−4 measured at
room temperature in the solid state.
which have been reported as an important factor contributing to
the emissive properties of coinage d10 metal complexes.39,40 So,
the different emissive behaviors may arise from the synergistic
effects of different factors, including coordination, modification
of amino groups, and Ag−Ag interactions, which may result in
the different HOMO−LUMO gaps. Upon irradiation with a
hand-held UV light (λ = 365 nm), the crystals of 1−4
respectively emit a cyan, blue-cyan, and fleshcolor light at
room temperature (Figure 3).
incorporation of [Ag−Ag]2+ cationic units. Moreover, the
argentophilic interactions are modulated by the uncoordinated
amino substituents. The study herein proves that modification
and subtle changes of the cage structures could be realized by a
one-pot synthetic method. The luminescent phenomenon of the
four complexes was investigated preliminarily and might be
attributed to a ligand-centered transition perturbed by a
synergistic effect.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.8b03388.
■
S
Experimental details, Figures S1−S11, and Tables S1 and
S2 (PDF)
Accession Codes
CCDC 1881631−1881634 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: +44 1223 336033.
Figure 3. Photographs of 1−4 (from left to right) crystals under a
daylight lamp (top) and UV light (λ = 365 nm; bottom).
AUTHOR INFORMATION
Corresponding Author
*E-mail: xxgk123@163.com (J.-P.M.).
ORCID
Guo-Xia Jin: 0000-0001-5554-6412
Jian-Ping Ma: 0000-0002-5300-3307
■
Photoluminescent spectra of L, L1, L2, and 1−4 were also
measured in the solution state (in dimethyl sulfoxide), as shown
in Figure 4. The free ligands L, L1, and L2 show emission
maxima at 473, 450, and 470 nm, respectively, while the cages
1−4 show emission maxima at 441, 450, 442, and 467 nm,
respectively, upon excitation at 380 nm. By comparison, the
emission peaks in the solution state blue-shift to some extent
compared to those in the solid state for all of the ligands and
complexes. These experimental results indicate that the
intermolecular interaction between the silver(I) cages result in
smaller HOMO−LUMO gaps in the solid state.
In conclusion, four Ag3L2 cylinder-like cages (1−4) with
three-stranded helical arms are constructed from a newly
designed tripodal ligand L and silver salts in different solvent
systems with/without liquid ketone. The formation of
coordination cages occurred simultaneously with the con-
densation of amino groups and ketone. The remarkable
structural feature of the cages 1−4 is their spontaneous
Author Contributions
‡These authors contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful for financial support from NSFC (Grants
21771120 and 21801127).
■
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