[Ag–Ag]2+ Unit-Encapsulated Trimetallic Cages: One-Pot Syntheses

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[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*,†

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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 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-pyridyl)-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 Xray diffraction (Figure S6 and Table S1). 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 fourcoordinate 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

ABSTRACT: 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.

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he chemistry of supramolecular coordination cages has 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 threedimensional (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-yl1,2,4-triazol-3-ylmercaptomethyl)-2,4,6-trimethylbenzene (L), and tetrahedral silver(I) centers in different solvent systems. The © XXXX American Chemical Society

Received: December 5, 2018

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DOI: 10.1021/acs.inorgchem.8b03388 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

pot synthetic method by introducing liquid ketone to the reaction systems. For tunately, 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 single-crystal X-ray diffraction (Figures S8−S10). 1H 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-2ylideneamino (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 condensation 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 configurations. 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 ligandcentered 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 unoccupied molecular orbital (LUMO) energy gap of the complexes,

Scheme 1. Synthetic Route of Cages 1−4

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 oneB

DOI: 10.1021/acs.inorgchem.8b03388 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 2. Photoluminescent spectra of L, L1, L2, and 1−4 measured at room temperature in the solid state.

Figure 4. Photoluminescent spectra of L, L1, L2, and 1−4 measured at room temperature in the solution state (in dimethyl sulfoxide).

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.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b03388. Experimental details, Figures S1−S11, and Tables S1 and S2 (PDF) Accession Codes

CCDC 1881631−1881634 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge 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).

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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 condensation of amino groups and ketone. The remarkable structural feature of the cages 1−4 is their spontaneous

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (J.-P.M.). ORCID

Guo-Xia Jin: 0000-0001-5554-6412 Jian-Ping Ma: 0000-0002-5300-3307 Author Contributions ‡

These authors contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful for financial support from NSFC (Grants 21771120 and 21801127). REFERENCES

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DOI: 10.1021/acs.inorgchem.8b03388 Inorg. Chem. XXXX, XXX, XXX−XXX