Anion-templated Self-assembly for the Preparation of Silver-t-butylthiolate Clusters
Jun-Ling JIN , Yang-Lin SHEN , Li-Wei MI , Yun-Peng XIE , Xing LU
Silver(I) thiolate clusters have attracted extensive attention due to structural diversity and potential applications in luminescence, sensors, medicine, and imaging to name a few[1-11]. However, the preparation of silver(I) thiolate clusters still follows a trial-and-error method and the uncontrollable syntheses remain the main barrier to produce specific clusters and further achieve these potentials that are mentioned above[12, 13]. Polymeric 1:1 silver thiolate coordination polymers [AgSR]n are often utilized as a precursor in the syntheses of clusters. However, under the action of solubilizing ligands[14], what kind of components such polymers will be cut into is still not clear and there are few related discussions[15, 16]. Of note, the template method could be used to capture and fix the polymer fragments in the solution, and the formed clusters provide the atomically precise structure to infer the species of polymer fracture[17, 18]. Anion templates such as halogen, sulfide, oxyacid, and polyoxometallate (POM) are applied to assist the assembly of silver thiolate clusters with [AgSR]n polymer fragments and different solubilizing ligands[19, 20].
Benefiting from the extraordinary solubleness with the addition of extra silver salts and solubilizing ligands, silver-t-butylthiolate polymer [AgtBuS]n has been widely used as precursors for the synthesis of silver clusters[21]. Many serendipitous silver-t-butylthiolate clusters were obtained, such as (CO3)@Ag20(tBuS)10, (W6O21)@Ag34(tBuS)26, Ag62S13(tBuS)32, and Ag320S130(tBuS)60[22-25]. To deepen the understanding of the self-assembly process of silver thiolate clusters, systematic cluster synthesis and single-crystal structure determination are urgently needed[26].
Herein, polymer [AgtBuS]n was chosen as the precursor for this systematic study of cluster assemblies. By reacting with N-donating ligands, a similar polymeric compound {[Ag6(tBuS)4]·2BF4}n (1) was obtained. Moreover, the provided template NO3− led to the formation of cluster [(NO3)@Ag19(tBuS)10(CF3CO2)8(4-cp)]·2H2O (4-cp = 4-cyano pyridine; 2). CO32− template was in situ generated from the fixation of atmospheric carbon dioxide and gave a larger cluster (CO3)@Ag20(tBuS)10(CF3CO2)8(CH3CN)4 (3) sharing the same structure pattern [AgtBuS]5 circles. In contrast, by introducing bulky and strong ligands (EtO)2PS2− and (iPrO)2PS2−[27-29], clusters (V2O7)@Ag22(tBuS)8[(EtO)2PS2]9·OH·H2O (4) and (W2O9)@Ag24(tBuS)14[(iPrO)2PS2]6·CH3OH (5) with extremely short [AgtBuS]n pieces were produced. In this work, we report the synthesis and crystal structures of five well-defined compounds 1~5, while attempt to clarify the possible [AgtBuS]n fragmented species and the actual starting point of cluster assemblies.
All reagents were purchased from commercial companies and used as received without further purification. [AgtBuS]n precursor was prepared according to the reported literature[30]. Elemental analyses for C and H were performed with a PerkinElmer 2400 elemental analyzer. Crystal data of 1~5 were collected on a Bruker D8 Quest diffractometer with Mo-Kα radiation. The multi-scan method was used for absorption corrections. The structures were solved by direct methods and refined with SHELXL-2014[31].
[AgtBuS]n (0.039 g, 0.2 mmol), AgBF4 (0.016 g, 0.08 mmol) and 1, 4-diazabicyclo[2.2.2]octane (0.010 g, 0.09 mmol) were dissolved in 6 mL CH3OH under ultrasonication. A colorless solution was collected by filtration and slow evaporation of this solution afforded the product as colorless crystals. Yield: ca. 12%. Elemental analysis (%) calcd. for Ag6S4C16H36F8B2: C, 16.32; H, 3.06. Found: C 16.14, H 3.17.
[AgtBuS]n (0.039 g, 0.2 mmol), AgNO3 (0.017 g, 0.1 mmol), AgCF3CO2 (0.022 g, 0.1 mmol) and 4-cyanopyridine (0.010 g, 0.096 mmol) were dissolved in 6 mL CH3OH/toluene (v: v = 1:1) under ultrasonication. A colorless solution was collected by filtration and slow evaporation afforded the product as light yellow crystals. Yield: ca. 21%. Elemental analysis (%) calcd. for Ag19S10C62H98O21N3F24: C, 18.40; H, 2.42. Found: C, 18.31; H, 2.54.
[AgtBuS]n (0.039 g, 0.2 mmol) and AgCF3CO2 (0.022 g, 0.1 mmol) were dissolved in 6 mL CH3CN under ultrasonication. A colorless solution was collected by filtration and slow evaporation of this solution afforded the product as colorless crystals. Yield: ca. 28%. Elemental analysis (%) calcd. for Ag20S10C65H102O19N4F24: C, 18.69; H, 2.44. Found: C, 18.58; H, 2.55.
[AgtBuS]n (0.039 g, 0.2 mmol) and AgBF4 (0.008 g, 0.04 mmol) were dissolved in 6 mL CH3OH under ultrasonication. Then (C2H5O)2PS2NH4 (0.004 g, 0.02 mmol) and Et4NVO3 (0.003 g, 0.008 mmol) were added under stirring to obtain a clear yellow solution. A yellow solution was collected by filtration and slow evaporation of this solution afforded the product as yellow crystals. Yield: ca. 15%. Elemental analysis (%) calcd. for Ag22S26C68H147O27P9V2: C, 16.39; H, 2.95. Found: C, 16.31; H, 3.02.
The synthetic processes of 5 were similar to that of 4, except that Et4NVO3 and (C2H5O)2PS2NH4 were replaced by Et4NWO4 (0.003 g, 0.006 mmol) and (iPrO)2PS2NH4 (0.004 g, 0.02 mmol). Yield: ca. 11%. Elemental analysis (%) calcd. for Ag24S26C92H210O21P6W2: C, 19.63; H, 3.73. Found: C, 19.56; H, 3.81.
Colorless crystals 1 and 3 with yellow crystals 2, 4 and 5 were selected for diffraction data collection on a Bruker Smart Apex3 CCD diffractometer equipped with a graphite-monochromatic MoKα radiation (λ = 0.71073 Å). Complex 1 crystallizes in orthorhombic, space group Ima2 with a = 8.0211(1), b = 17.506(3), c = 25.923(4) Å, V = 3640.1(10) Å3, Z = 4, C16H36B2F8S4Ag6, Mr = 1177.53, F(000) = 2240, Dc = 2.149 Mg/m3 and µ = 3.442 mm-1. A total of 8631 reflections were collected for 1, of which 2895 (Rint = 0.0360) were independent in the range of 2.808≤θ≤25.022º for 1 by using a φ-ω scan mode. Complex 2 is of monoclinic system, space group P21/n with a = 28.993(3), b = 13.3666(1), c = 30.602(3) Å, β = 103.405(2)º, V = 11536.4(19) Å3, Z = 4, C62H98F24N3O21S10Ag19, Mr = 4047.56, F(000) = 7712, Dc = 2.330 Mg/m3 and µ = 3.416 mm-1. A total of 64135 reflections were collected for 2, of which 16493 (Rint = 0.0272) were independent in the range of 2.783≤θ≤23.257º for 2 by using a φ-ω scan mode. Complex 3 crystallizes in space group P
The structures of complexes 1~5 were solved by direct methods with SHELXTL XT-2014 program and refined by full-matrix least-squares techniques on F2 with SHELXL-2014. The final R = 0.0419, wR = 0.1033 (w = 1/[σ2(Fo2) + (0.1138P)2 + 4.9551P], where P = (Fo2 + 2Fc2)/3), Rint = 0.0360, (Δ/σ)max = 0.000, S = 1.080, (Δρ)max = 0.0648 and (Δρ)min = –0.941 e/Å3 for 1. The final R = 0.0735, wR = 0.2067 (w = 1/[σ2(Fo2) + (0.1138P)2 + 4.9551P], where P = (Fo2 + 2Fc2)/3), Rint = 0.0272, (Δ/σ)max = 0.000, S = 1.056, (Δρ)max = 2.584 and (Δρ)min = –1.425 e/Å3 for 2. The final R = 0.0583, wR = 0.1550 (w = 1/[σ2(Fo2) + (0.1138P)2 + 4.9551P], where P = (Fo2 + 2Fc2)/3), Rint = 0.0478, (Δ/σ)max = 0.000, S = 1.087, (Δρ)max = 1.855 and (Δρ)min = –2.255 e/Å3 for 3. The final R = 0.0704, wR = 0.1701 (w = 1/[σ2(Fo2) + (0.1138P)2 + 4.9551P], where P = (Fo2 + 2Fc2)/3), Rint = 0.0637, (Δ/σ)max = 0.000, S = 0.993, (Δρ)max = 1.192 and (Δρ)min = –0.815 e/Å3 for 4. The final R = 0.0845, wR = 0.2050 (w = 1/[σ2(Fo2) + (0.1138P)2 + 4.9551P], where P = (Fo2 + 2Fc2)/3), Rint = 0.0458, (Δ/σ)max = 0.000, S = 0.958, (Δρ)max = 1.938 and (Δρ)min = –1.702 e/Å3 for 5.
The synthetic details are provided in the experimental section. The [AgtBuS]n precursor is generally insoluble in solvents, and its structure is predicted to be a supramolecular polymer where the monomers are end-to-end connected via Ag−S bonding and further stabilized by the so-called metallophilic attractions[15, 32]. After reacting with different silver salts in the presence of solubilizing ligands, the [AgtBuS]n chain structure is intercepted, and the following rearrangement and self-assembly of [AgtBuS]n fragments are significantly affected by the templates during the synthesis[33]. Initially, [AgtBuS]n precursor reacted with 1, 4-diazabicyclo-[2.2.2]octane ligands, forming {[Ag6(tBuS)4]}n that retained the end-to-end pattern of [AgtBuS]n precursor. Although the 1, 4-diazabicyclo[2.2.2]octane ligand does not appear in the final structure, in the absence of this ligand, the compound {[Ag6(tBuS)4]}n cannot be obtained. Moreover, through intervention of NO3− and CO32− templates, clusters NO3@Ag19 and CO3@Ag20 were isolated. Both of them exclusively contain [AgtBuS]5 structural units. In contrast, bulky and strong ligands (EtO)2PS2− and (iPrO)2PS2− support the generation of V2O7@Ag22 and W2O9@Ag24 with extremely short [AgtBuS]n pieces, which in turn proves that solubilizing ligands affect the fragmentation of [AgtBuS]n chain and change the actual starting point of the assembly.
X-ray crystallography results reveal that compound 1 crystallizes in the orthorhombic Ima2 space group, and it was identified as a polymeric species {[Ag6(tBuS)4]·2BF4}n. As displayed in Fig. 1, compound 1 with an exclusive μ3-η1η1η1 coordination of tBuS− bridging three silver ions presents a tubular structure with about 1 nm diameter. The Ag−S bond lengths in 1 range from 2.366 to 2.415 Å. To the best of our knowledge, the structure of the precursor is predicted as chain-like [AgtBuS]n with μ2-η1η1 coordination of the tBuS− (Fig. 1d)[15]. Thus, the formation of 1 may involve the fusion of four [AgtBuS]n chains by generating S−Ag−S bridges while the extra required silver ions are provided by AgBF4 salts[34].
By introducing NO3− template, compound 2 was obtained from the mother liquor. This species crystallizes in monoclinic space group P21/n (Fig. 2b). Compound 2 was determined as [(NO3)@Ag19(tBuS)10(CF3CO2)8(4-cp)]·2H2O. The NO3− template is encapsulated by Ag19(tBuS)10 unit, which generates from the assembly of a Ag9 circle and two [AgtBuS]5 synthons in a sandwich way. The anionic NO3− template builds electrostatic interactions with positively charged silver ions to form the silver-rich entity Ag9, which is further consolidated by the [AgtBuS]5 synthons that are assigned to [AgtBuS]n fragment. The Ag−S and Ag···Ag bond lengths are in the range of 2.365~2.643 and 2.919~3.358 Å, respectively.
Color codes: Ag, pink and green; S, yellow; C, grey; O, red; N, blue; F, light green
As the NO3− was replaced by a CO32− molecule, the crystals of 3 were prepared. Single-crystal XRD result reveals a neutral disk-like (CO3)@Ag20(tBuS)10(CF3CO2)8(CH3CN)4 structure of 3, and the same skeleton structure has been reported by the Sun and Zhou et al[22, 35]. 3 has a core-shell structure containing a CO32− core and a Ag20(tBuS)10-(CF3CO2)8(CH3CN)4 shell (Fig. 3). The Ag20 silver cage also consists of a Ag10 circle and two [AgtBuS]5 synthons in a sandwich way, which is almost the same as the structure of NO3@Ag19 except that the Ag20 silver cage displays a bigger Ag10 circle. This phenomenon could be ascribed to the CO32− template bearing more charges than that of NO3−, which is consistent with the conclusion suggested by Liu et al about the preparation of the templated silver alkynyl clusters[36].
Color codes: Ag, pink and green; S, yellow; C, grey; O, red; N, blue; F, light green
When Et4NVO3 was used as precursors, the template V2O74− was in situ generated, leading to the formation of 4. It crystallizes in triclinic space group P
The hydrogen atoms are omitted for clarity. Color codes: Ag, pink and green; S, yellow; C, grey; O, red; P, orange; V, indigo
Similarly, as (EtO)2PS2− and V2O74− were replaced by (iPrO)2PS2− and W2O94−, discrete cluster 5 was produced. As portrayed in Fig. 5, the structure of 5 was revealed by X-ray crystallography with all 24 Ag ions, 14 tBuS− ligands, and 6 (iPrO)2PS2− anions as well as a W2O94− in the interior. It crystallizes in the hexagonal P63/m space group. 5 exhibits a barrel-like structure, arising from the silver ions arranged as a Ag3−Ag6−Ag6−Ag6−Ag3 five-layer configuration. The external 14 tBuS− ligands show diverse coordination modes, 6 in µ2-ƞ1ƞ1; 2 in µ3-ƞ1ƞ1ƞ1; 6 in µ4-ƞ1ƞ1ƞ1ƞ1. Interestingly, there is a [AgtBuS]6 circle in the middle layer of 5, but the remaining 8 tBuS− ligands present an isolated distribution without forming likewise RS−Ag−SR bonding pattern, which is consistent with the finding in the structure of 4. Besides, ligands (iPrO)2PS2− display an exclusive µ3-ƞ1ƞ2 coordination mode with Ag−S bond lengths ranging from 2.434 to 2.492 Å. Besides, the in situ generated W2O94− resides in the silver cage and interacts with Ag ions by a µ15-ƞ1ƞ1ƞ1ƞ2ƞ2ƞ2ƞ2ƞ2ƞ2 mode with Ag−O distances of 2.339~2.514 Å.
The hydrogen atoms are omitted for clarity. Color codes: Ag, purple and green; S, yellow; C, grey; O, red; P, orange; W, rose
In summary, we have assembled and structurally determined five silver-t-butylthiolate compounds. Based on these atomically precise structures, we explore the actual starting species of the cluster self-assembly process in which the [AgtBuS]n polymer participates with different solubilizing ligands. As the provided solubilizing reagents have weak coordination ability, the obtained polymeric compound retains the end-to-end pattern of [AgtBuS]n precursor. Meanwhile, when NO3− and CO32− are applied, [AgtBuS]5 circles that may be transferred from soluble [AgtBuS]n fragments are found in NO3@Ag19 and CO3@Ag20. In contrast, (EtO)2PS2− and (iPrO)2PS2− anions have large size and strong coordination ability rendering the structure of the polymer completely fragmented. Therefore, extremely short [AtBuS]n pieces with silver ions assemble around the templates V2O74− and W2O94−, leading to the formation of clusters V2O7@Ag22 and W2O9@Ag24. This work focuses on the actual starting species of the solution self-assembly of classical cluster synthesis, but more research work is needed to clarify this problem.
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Figure 1 (a, b) X-ray structure of 1 viewed along the a and b axes, (c) Coordination mode of tBuS− ligands, (d) Predicted structure of [AgtBuS]n with the hydrogen atoms omitted for clarity. Color codes: Ag, pink and green; S, yellow; C, grey
Figure 2 (a) Structure of [AgtBuS]5 synthon, (b) X-ray structures of 2. The hydrogen atoms are omitted for clarity.
Color codes: Ag, pink and green; S, yellow; C, grey; O, red; N, blue; F, light green
Figure 3 X-ray structure of 3. The hydrogen atoms are omitted for clarity.
Color codes: Ag, pink and green; S, yellow; C, grey; O, red; N, blue; F, light green
Figure 4 (a, b) Structures of [AgtBuS]n fragments and V2O74− template, (c) X-ray structures of 4.
The hydrogen atoms are omitted for clarity. Color codes: Ag, pink and green; S, yellow; C, grey; O, red; P, orange; V, indigo
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