Three Silver Coordination Polymers with Diverse Architectures

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Three Silver Coordination Polymers with Diverse Architectures Constructed from Pyridine Carboxylic Hydrazide Ligands Shu-Han Lu,‡ Yuan Li,‡ Shao-Xiong Yang, Rui-Dun Zhao, Zhi-Xiang Lu, Xiao-Lan Liu, Yu Qin, Li-Yan Zheng,* and Qiu-E Cao*

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Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Functional Molecules Analysis and Biotransformation Key Laboratory of Universities in Yunnan Province, School of Chemical Science and Technology, Yunnan University, Kunming 650091, People’s Republic of China S Supporting Information *

ABSTRACT: A series of silver coordination polymers (CPs) have been synthesized through self-assembly of three pyridinecarboxylic acid hydrazide (p-, m-, o-position) ligands with silver clusters (named Ag1-iah, Ag2-iah, and Ag3-iah). These silver CPs show different one- and two-dimensional topologies including cross-helical chains, planar network, and parallel helical chains for Ag1-iah, Ag2-iah, and Ag3-iah, respectively. The combination of experimental and computational results reveals the critical role in the space distribution of the coordination site of silver clusters and ligands in controlling the silver CPs’ dimensionality and packing arrangement and modulating the optical properties and stability. Luminescent investigations reveal that Ag3-iah can selectively detect dichloromethane or trichloromethane in tetrachloromethane. These silver CPs provide a good model to study the influence of the space distribution of the coordination site of ligands on their packing arrangement and properties.

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which not only have a crucial influence on the final architectures but also show interesting electrical and luminescence properties.26−34 The rigid nitrogen-containing heterocyclic N-donor ligands possess a certain rigidity and stability, which can reduce the uncertainty in the assembly process and obtain the designed architectures.35−37 However, the N-donor ligands of alkylamine may take flexible coordination modes, which benefits the complexity of the resulting silver CPs.38,39 Among the nitrogen-containing heterocyclic ligands, pyridine derivatives are one of the most popular ligands. The metal−pyridine coordination bond is one of the most suitable systems for the self-assembly of welldesigned structures because of the formation of labile and reversible bonds as well as the diversity of ligand design.40−43 Recently, silver clusters, such as Ag10, Ag12, and Ag14, have been shown to assemble into one-, two-, and three-dimensional frameworks in which the silver clusters nodes were connected by pyridyl-type organic linkers.44−46 Further substituting the H of pyridine ring with carboxylic hydrazide (formylhydrazine) can not only generate carboxylic hydrazide (pyridinecarboxylic acid hydrazide) with different substituent positions, but also construct novel spatial structures with flexible chains. Besides, nitrogen atoms of the formylhydrazine can display supramolecular interactions, such as intermolecular and intra-

INTRODUCTION In the past two decades, coordination polymers have attracted more and more interest because of their fascinating and adjustable architectures and physicochemical properties.1−3 The ability to modulate the coordination number of coordination polymers (CPs) affords access to distinct secondary building units (SBUs) with assorted geometries and connectivities. The properties of CPs are highly dependent on their constituent metals, organic ligands, and space structure. For example, the luminescent chemical-sensing properties of CPs mainly rely on supramolecular interactions with guest species via coordination bonds, hydrogen bonding, and π−π interactions.4−9 Therefore, the development of novel CPs will lead to unexplored functions and applications. In particular, silver-based CPs are very attractive owing to the unpredictable coordination preferences of the metal center and the formation of significant Ag···Ag interactions, or so-called argentophilicity,10−12 which largely contributes to the formation of fascinating silver aggregations and benefits the structural diversity and attractive optoelectronic properties. Silver clusters with atomic precision represent a versatile type of building block with abundant coordination site,13−16 which has been successfully applied for the preparation of CPs based on silver clusters complexes (shortly as silver CPs) with amazing optoelectronic properties.17−25 On the other side, N-donor ligands have showed fundamental interest as linkers for silver CPs construction, © XXXX American Chemical Society

Received: June 26, 2019

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DOI: 10.1021/acs.inorgchem.9b01874 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Table 1. Crystal Data and Structure Refinement Summary for Ag1-iah, Ag2-iah, and Ag3-iah silver CPs formula formula weight temperature/K crystal system space group a/Å b/Å c/Å α/° β/° γ/° V/Å3 Z ρcalc, g/cm3 μ/mm−1 F(000) index ranges

GOF on F2 final R indexes [I ≥ 2σ(I)] R indices (all data)

Ag1-iah

Ag2-iah

Ag3-iah

C24H37Ag5F6N4O5S3 1211.10 173 monoclinic C2/c 27.055(3) 16.7198(19) 18.698(2) 90 94.502(2) 90 8432.1(17) 8 1.908 2.490 4688.0 −35 ≤ h ≤ 30 −21 ≤ k ≤ 21 −24 ≤ l ≤ 23 1.045 R1 = 0.0553, wR2 = 0.1583 R1 = 0.0821, wR2 = 0.1808

C26H40Ag5F6N5O5S3 1252.16 220 monoclinic P21/n 15.8445(14) 16.3701(14) 17.0804(15) 90 111.842(2) 90 4112.2(6) 4 2.023 2.557 2432.0 −17 ≤ h ≤ 19 −20 ≤ k ≤ 20 −20 ≤ l ≤ 21 1.032 R1 = 0.0380, wR2 = 0.1046 R1 = 0.0506, wR2 = 0.1138

C46H71Ag10F12N7O10S6 2381.15 220 monoclinic P21/c 12.6074(12) 27.316(3) 25.206(3) 90 101.714(3) 90 8499.8(14) 4 1.861 2.468 4600.0 −15 ≤ h ≤ 15 −33 ≤ k ≤ 33 −29 ≤ l ≤ 30 1.028 R1 = 0.0937, wR2 = 0.2753 R1 = 0.1445, wR2 = 0.2917

molecular hydrogen bonds.47−49 In this sense, N-donor ligands provide a more ideal platform to investigate the structure− property relationship of silver CPs. Indeed, studies on controlling assembled networks with atomic-level precision by different space distributions of the coordination site of ligands, containing both rigid and flexible coordination modes, are believed to affect the dimensionality and resulting properties and have not been fully investigated yet. In the present study, we have designed and synthesized three silver CPs by coordinating three pyridine carboxylic hydrazide (4-pyridine carboxylic hydrazide (p-iah), 3-pyridine carboxylic hydrazide (m-iah), and 2-carboxylic hydrazide (o-iah) with silver nanoclusters. These ligands not only possess both rigid and flexible N-donor but also display different spatial structures, which are beneficial to systematically investigating the structure−property relationship. The formulas of these three silver CPs were certified by single crystal X-ray diffraction (SXRD) to be [Ag 1 0 (CF 3 COO) 4 (S t Bu − ) 6 (p-iah) 2 (CH3CN)2]n, [Ag10(CF3COO)4(StBu−)6(m-iah)4(CH 3 CN) 4 ] n , and [Ag 10 (CF 3 COO) 4 (S t Bu − ) 6 (o-iah) 4 (CH3CN)]n, whose structures displayed cross-helical chains, planar network, and parallel helical chains, respectively. These silver CPs are subsequently characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis, absorption spectroscopy, photoluminescence spectroscopy, and theoretical calculations. These data reveal that the space distribution of coordination site of ligands is very important for structures and properties of these silver CPs. Furthermore, Ag3-iah can selectively detect dichloromethane or trichloromethane in tetrachloromethane solvent.

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Powder X-ray diffraction (PXRD) measurement was performed on a TTRIII X-ray diffractometer (Rigaku, Japan) with Mo Kα radiation at 40 kV and 200 mA. FTIR spectra were recorded in the range 4000− 400 cm−1 on a Thermo Nicolet spectrometer by using KBr pellets. Thermogravimetric analysis (TGA) was performed on a NETZSCH STA 449F3 instrument with a heating rate of 10 °C·min−1 under a nitrogen atmosphere. The solid-state UV−vis absorption was characterized using a UV/vis/NIR spectrophotometer (UV-3600 Plus, Shimadzu, Japan). X-ray single crystal diffraction (SXRD) measurement was performed on Bruker APEX-II CCD (Mo X-ray source). All calculations were performed using the Gaussian 09 program. All the structures were completely optimized using a combined basis set: the LanL2DZ basis set was used for Ag along with the 6-31G(d) basis set for C, N, H, F, S, and O. Synthesis of AgStBu−. AgStBu− was prepared according to published protocols.50 Synthesis of Ag1-iah, Ag2-iah, and Ag1-iah. AgStBu (0.1086 g, 0.55 mmol) and AgCF3COO (0.0607 g, 0.28 mmol) were dissolved in mixed solvent of acetonitrile and ethanol with the ratio of 1:1 under ultrasound to obtain the Ag12 nanocluster [Ag12(StBu−)6(CF3COO)6(CH3CN)6], and then the corresponding pyridinecarboxylic hydrazide ligands (p-iah, m-iah, o-iah) (0.0590 g, 0.5 mmol) were added. The obtained solution slowly evaporated at the temperature of 5−10 °C to get colorless crystals after a week, which were washed with diethyl ether, filtered, and dried in air. On the basis of the silver element, the yields of Ag1-iah, Ag2-iah, and Ag3-iah were 43%, 56%, and 26%, respectively. Crystal Data Collection and Refinement. The crystal data of Ag1-iah, Ag2-iah, and Ag3-iah were collected on a Bruker APEX-II CCD diffractometer at room temperature using Mo Kα radiation (λ = 0.71073 Å). The single-cell determination procedure was adopted by Bruker Advanced. Empirical absorption corrections were applied using the SADABS program. The structure was resolved and refined by the SHELX-97 software. Data were reduced by the Bruker SAINT package. The crystal system and space group of crystal were verified by the PLATON subroutine ADDSYM SHELX PLATON program. The structures were further refined using the SHELXL-97 by fullmatrix least-squares for non-hydrogen atoms with anisotropy. The hydrogen atoms in organic ligands are produced geometrically

EXPERIMENTAL SECTION

Materials and Physical Measurements. Commercially available chemicals were purchased and used without further purification. B

DOI: 10.1021/acs.inorgchem.9b01874 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry symmetrically. Hydrogen atoms were placed in calculated positions and refined using the riding model. Details of the crystal data are listed in Table 1. Selected bond lengths, angles, and hydrogen bonds are given in Tables S4−S6. Crystallographic data were deposited in the Cambridge Structural Date Centre (CCDC) and can be obtained free of charge at http://www.ccdc.cam.ac.uk/ by using reference numbers 1906314−1906316 (Ag1-iah, Ag2-iah, and Ag3-iah, respectively).

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RESULTS AND DISCUSSION Structure of Ag1-iah. The crystal data revealed Ag1-iah crystallized in the monoclinic with the space group C2/c. The point-symmetric structural unit of Ag1-iah consists of 10 Ag(I), 4 ligands CF3COO−, 6 ligands StBu−, 2 CH3CN molecules, and 2 p-iah molecules. As presented in Figure 1A, Figure 2. (A) The core of the structural unit of Ag2-iah. (B) The structural unit of Ag2-iah. (C) Spatial stacking diagram of Ag2-iah. (D) Topology diagram of Ag2-iah with organic ligands simplified.

Structure of Ag3-iah. The crystal Ag3-iah crystallizes in the monoclinic P21/n space group. Each structural unit Ag3iah consists of 10 Ag(I), 4 CF3COO−, 6 StBu−, 1 CH3CN molecule, and t2 o-iah molecules, and the core of structural unit of Ag3-iah is also Ag10S6. How Ag3-iah differs from Ag1iah and Ag2-iah is the asymmetrical structural unit (Figure 3A), which was caused by the stronger stereohindrance and

Figure 1. (A) The core of the structural unit of Ag1-iah. (B) The structural unit of Ag1-iah. (C) Spatial stacking diagram of Ag1-iah. (D) Topology diagram of Ag1-iah with organic ligands simplified.

after being simplified, the core of the structural unit is a threelayer structure composed of 10 Ag(I) and 6 S atoms. The head and tail layers of the three-layer structure are both zigzag hexagons formed by Ag−S bonds, and the middle layer is a parallelogram formed by Ag−Ag interactions (2.9369−3.2230 Å, less than 3.44 Å), indicating significant argentophilic interactions. As shown in Figure 1B, Ag(I) in Ag1-iah has five coordination forms. The specific coordination environment of Ag (I) is shown in Supporting Information (Table S4). According to the above coordination forms, the p-iah molecule bridged structural units through Ag−N bonds to form an infinite 1D chain (Figure 1C). The adjacent chains intersected with each other to form a cross-helical chains structure, as shown in Figure 1D. Structure of Ag2-iah. The Ag2-iah crystallizes in the monoclinic P21/n space group. Each structural unit consists of 10 Ag (I), 4 CF3COO−, 6 StBu−, 4 CH3CN molecules, and 2 m-iah. Similar to the silver CP Ag1-iah, the core of the structural units is also a three-layer structure, in which the head and tail layers are the crown-like hexagons formed by Ag−S bonds, and the middle layer is a parallelogram formed by Ag− Ag interactions (3.0277−3.2006 Å) (Figure 2A). As shown in Figure 2B, in the coordination silver CP Ag2-iah, Ag atoms have five coordination forms. The specific coordination environment of Ag(I) is shown in Supporting Information (Table S5). As depicted in Figure 2C, the structural units are linked by m-iah through Ag−N bonds to form a 2D zigzag mesh structure, which is different from the 1D chain structure of silver CP Ag1-iah (Figure 2D).

Figure 3. (A) The core of the structural unit of Ag3-iah. (B) The structural unit of Ag3-iah. (C) Spatial stacking diagram of Ag3-iah. (D) Topology diagram of Ag3-iah with organic ligands simplified.

space charge effects of the ligands o-iah. Ag(I) in Ag3-iah have 10 coordination forms, and the specific coordination environment of Ag(I) is shown in Supporting Information (Table S6). On the basis of the coordination forms above, o-iah molecules bridged the structural units by Ag−N bonds to form a 1D chain structure (Figure 3C). Unlike the silver CP Ag1-iah, the chains of Ag3-iah are parallel. It is clear to observe the presence of hydrogen bonds (N−H···O) in Ag3-iah (Figure S1). The simplified topology diagram of Ag3-iah is shown in Figure 3D. Space Distribution of Coordination Site on the Structure of Silver CPs. The structures of three silver CPs are entirely distinctive, which could be attributed to the C

DOI: 10.1021/acs.inorgchem.9b01874 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry different spatial distributions of the coordination site on the silver cluster and ligands. Each silver cluster of all three silver CPs includes 10 Ag (I), and 4 of them coordinated with iahligands. To determine the factors influencing the space distribution of the coordination site on silver clusters, we measured the distance of the Ag−Ag within one silver cluster for three silver CPs, respectively. For point-symmetric Ag1-iah and Ag2-iah, the distance of Ag−Ag in the opposite angle is the farthest. For asymmetric Ag3-iah, all Ag−Ag distances were measured. Combining with the crystal data, we found the four Ag(I) coordinated with ligands are two pairs of Ag(I) (Noted by “√”) with the farthest distances (Tables S1−S3) for three silver CPs. In addition, the connecting modes of two ligands coordinated with Ag(I) on the same side are entirely adverse. One of them is linked to Ag(I) (Ag2 for Ag1-iah; Ag3 for Ag2iah; Ag3 and Ag5 for Ag1-iah) by the rigid N atom of pyridine, and the other is linked to Ag(I) (Ag3 for Ag1-iah; Ag1 for Ag2iah; Ag2 and Ag4 for Ag1-iah) by the flexible terminal N atom of formylhydrazine (Figure 4A−C). Both of the farthest distances of the Ag(I) coordinated site and the inverse arrangement of ligands are beneficial for less steric hindrance. In terms of ligands, the spatial location of rigid and flexible N coordination site of o, m, and p-iah is distinctive. Combining the discussion on the space distribution of the coordination

site on clusters, we could measure the spatial distances of two terminal N atoms from ligands which are closer to each other. The spatial distances are 6.2022 Å (N1···N3, Figure 4A), 13.8203 Å (N1···N3, Figure 4B), and 5.3280 Å (N3···N4, Figure 4C), respectively. The distances for Ag1-iah and Ag3iah are close to the size of the silver clusters, while the distance for Ag2-iah is much larger than the size of its silver cluster. As a consequence, for Ag1-iah and Ag3-iah, two terminal N atoms of ligands on the same side coordinated with the same silver cluster, and finally 1D chains formed. For Ag2-iah, the terminal N atoms of ligands were away from each other, resulting in their coordination with different silver clusters. Consequently, the divergent growth pattern leads to the 2D zigzag mesh structure. Fundamentally, the space distribution of the coordination site on silver clusters and N coordination site of ligands interacted with each other and eventually led to the diverse structures of three silver CPs, which disclosed the important impact of ligands on the forming of silver CPs. Other Characterizations. In order to further investigate the structures of these three coordinate silver CPs, other characterizations were conducted. First, the FTIR spectrum of Ag12, ligands, and silver CPs was recorded at room temperature (Figures S2 and S3). Compared with that of ligands, the characteristic peak of ν (N−H) around 3200 cm−1 disappeared in the FTIR spectrum of silver CPs, indicating that amino groups of formyl hydrazine were coordinated with Ag(I) (Figure S3). The ν (CN) bands of pyridines (1580 cm−1, 1520 cm−1, 1450 cm−1) from ligands all changed after coordination, which revealed the coordination between N atoms from pyridines and Ag(I). All these results were in accordance with crystal data analysis. The intensity of peak ν (CO) at 1780 cm−1 increased obviously in the spectra of Ag3-iah, further suggesting the carbonyl of formyl hydrazine took part in the coordination.51,52 However, the abovementioned enhancement was not observed in the spectrum of Ag1-iah and Ag2-iah, further supporting the presence of hydrogen bonds in Ag3-iah. According to the powder X-ray diffraction patterns of three silver CPs, the crystallinity and phase purity of these silver CPs were confirmed (Figure S4). To monitor the thermal stability of these silver CPs, thermogravimetric analysis measurements were conducted. As shown in Figure S5, the main weight loss for three silver CPs occurs at 110, 125, and 150 °C, respectively, which could be attributed to the decomposition of the building blocks of Ag clusters. The results show that Ag2-iah is more thermally stable than others, probably due to the 2D zigzag mesh structure. Fluorescence and Absorption Properties of silver CPs. The solid-state fluorescence spectra were measured at ambient conditions, showing the maximum emission at 535 nm (λex = 370 nm) and 525 nm (λex = 375 nm) for Ag1-iah (Figure 5A) and Ag2-iah (Figure 5B), respectively. Strikingly, Ag3-iah displayed two states of fluorescence: the maximum excitation wavelength of freshly prepared Ag3-iah is 535 nm excited at 375 nm (Figure 5C). However, as shown in Figure 5D, after it was soaked in low-polarity solvent (such as diethyl ether and tetrachloromethane), the maximum emission wavelength of solid-state fluorescence was red-shifted to 545 nm (λex = 370 nm). This phenomenon did not exist in two other silver CPs, which revealed the important role of ligands in the fluorescence properties of silver CPs. Furthermore, the UV−vis absorption spectra demonstrated that the maximum absorption wavelengths of Ag1-iah, Ag2-iah, and Ag3-iah were

Figure 4. Simplified structural unit of (A) Ag1-iah, (B) Ag2-iah, and (C) Ag3-iah reserving the C, N, and O atoms of p-, m-, and o-iah. D

DOI: 10.1021/acs.inorgchem.9b01874 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

(Figure 6C,D). As for Ag3-iah, the excitation transitions demonstrated the fluorescence emission mechanism was speculated to be the combination of MLCT and ligand− ligand charge transfer (LLCT) (Figure 6E,F).57,58 The stability of these silver CPs was further investigated by recording the fluorescent intensity after different times at room temperature. As shown in Figure S8, Ag1-iah and Ag3-iah displayed satisfactory stability and remained 70% and 80% after one month, which was favorable for their further application. In view of the unique fluorescence properties of Ag3-iah, the fluorescence behaviors of Ag3-iah in various solvents were further studied. We found that Ag3-iah exhibited weak green fluorescence in high-polarity solvents but strong yellow fluorescence in low-polarity solvents. For example, Ag3-iah exhibited weak green fluorescence in high-polarity solvents such as dichloromethane and trichloromethane, while it showed strong yellow fluorescence in relatively low-polarity tetrachloromethane (Figure S9). The recycled experiment confirmed that Ag3-iah almost held a stable solvent effect over four cycles (Figures S10 and S11). To make sure whether the structure of Ag3-iah changed in these solvents, we measured the XRD of Ag3-iah after being soaked in solvents with different polarities (CH2Cl2, CHCl3, CCl4) for 3 h, respectively (Figure S12). The PXRD patterns revealed that the structure of Ag3-iah remained unchanged after being soaked in these solvents. Thus, we conducted further investigation of the determination of dichloromethane or trichloromethane in tetrachloromethane solvent. First, the fluorescence emission spectra of Ag3-iah immersed in dichloromethane/tetrachloromethane mixed solvents were measured. As shown in Figure 7A, the fluorescent intensity of

Figure 5. Solid-state fluorescence spectra of Ag1-iah (A), Ag2-iah (B), Ag3-iah (C), and Ag3-iah (D) after soaking with low-polar solvents.

380, 380, and 375 nm, respectively (Figure S6). These results are in accordance with the maximum excitation wavelengths of their fluorescent excitation emission spectra. In addition, to explore the fluorescence emission mechanism of the silver CPs, theoretical calculations on their energy levels were carried out by means of TD-DFT calculations. All the geometry optimizations and frequency calculations were performed by using the B3LYP (6-31G* for C, H, O, N, F, S) combination with the LanL2DZ (for Ag). We performed TD-DFT calculations and obtained the simulated UV−vis absorption spectra (Figure S7), which was in good agreement with the experimental UV−vis absorption spectra. The excitation transitions (HOMO → LUMO) based on TDDFT calculations for Ag1-iah suggested a mixture of local excitation (LE) and metal−ligand charge transfer (MLCT) (Figure 6A,B).53−56 Likewise, the fluorescence emission mechanism of Ag2-iah is also assigned to be LE and MLCT

Figure 7. Fluorescence emission spectra of Ag3-iah in tetrachloromethane with the various volume fractions of dichloromethane (A) and trichloromethane (C), respectively. Linear plot of fluorescence intensity versus the volume fractions of dichloromethane (B) and trichloromethane (D) in tetrachloromethane, respectively.

Ag3-iah linearly decreased when the volume fraction of dichloromethane increased. When the volume fraction of dichloromethane ramped up to 45%, the fluorescence intensity of Ag3-iah became one-fifth of the initial one (Figure 7A). There was a good linear relationship between fluorescence intensity and the dichloromethane content in the solvent mixture ranging from 10% to 45% (Figure 7B), and the detection limit is 3.08%. Likewise, with the volume proportion of trichloromethane increased in the range from 5% to 60% in trichloromethane/tetrachloromethane mixed solvents, the

Figure 6. The HOMO (A) and LUMO (B) orbits of Ag1-iah. The HOMO (C) and LUMO (D) orbits of Ag2-iah. The HOMO (E) and LUMO (F) orbits of Ag3-iah. E

DOI: 10.1021/acs.inorgchem.9b01874 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry fluorescence intensity of Ag3-iah gradually reduced. When the volume proportion of trichloromethane was up to 60%, the fluorescence intensity decreased to be about one-tenth of the blank one (Figure 7C). The fluorescence intensity exhibits a great linear correlation with the volume fraction of trichloromethane at this range (Figure 7D), and the detection limit is 2.27%. These results further demonstrated the potential application of Ag3-iah in determination of dichloromethane or trichloromethane in tetrachloromethane solvent.

Young Talents Training Programs( C176220200) of Yunnan University.

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CONCLUSIONS In summary, three silver CPs with diverse architectures have been obtained by introducing pyridine carboxylic hydrazide (p-, m-, o-position) ligands into silver clusters. By employing the space distribution of the coordination site, we successfully achieved the controlled assembly of two well-defined, onedimensional silver CPs (Ag1-iah and Ag3-iah) and one clusterbased assembled network (Ag2-iah), with atomic-level control over the packing arrangement and dimensionality. Furthermore, Ag3-iah can selectively be applied as a fluorescent sensor for organic solvent. The investigation in the structures of these silver CPs provides a model for designing and preparing different silver coordination networks by adjusting the space distribution of the coordination site to gain the on-demand properties.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b01874. Additional structures and coordination angles and hydrogen-bonds interactions; the diagram stability of fluorescence intensity; FTIR spectra, PXRD patterns, TGA curves, UV−vis absorption spectr,a and simulated UV−vis absorption spectra fluorescence emission spectra of Ag3-iah in dichloromethane, trichloromethane, and tetrachloromethane, important bond lengths (PDF) Accession Codes

CCDC 1906314−1906316 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.

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AUTHOR INFORMATION

Corresponding Authors

*(L.-Y.Z.) E-mail: [email protected]. *(Q.-E.C.) E-mail: [email protected]. ORCID

Li-Yan Zheng: 0000-0002-3726-1568 Author Contributions ‡

S.-H.L. and Y.L. contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (NSFC, 21765024) and the F

DOI: 10.1021/acs.inorgchem.9b01874 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.9b01874 Inorg. Chem. XXXX, XXX, XXX−XXX