Cobalt- and Nickel-Containing Germanotungstates Based on Open

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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

Cobalt- and Nickel-Containing Germanotungstates Based on Open Wells−Dawson Structure: Synthesis and Characterization of Tetrameric Anion Kaili Dong, Pengtao Ma, Hechen Wu, Yuke Wu, Jingyang Niu,* and Jingping Wang*

Inorg. Chem. Downloaded from pubs.acs.org by UNIV OF LOUISIANA AT LAFAYETTE on 04/25/19. For personal use only.

Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, China S Supporting Information *

ABSTRACT: Two transition-metal-substituted compounds K10H10{[Co(H2O)2]2[Co(H2O)3]2(Ge4W36O130)}·32H2O (1Co) and K10H10{[Ni(H2O)2]2[Ni(H2O)3]2(Ge4W36O130)}·32H2O (2Ni), have been successfully synthesized, both of which consist of the S-shaped tetrameric structure {Ge4W36} constructed from trivacant Keggin-type germanotungstate precursor K8Na2[A-α-GeW9O34]·25H2O. These compounds were characterized by single crystal X-ray diffraction crystallography, X-ray powder diffraction (XRD), Raman spectra, thermogravimetric analysis (TGA), electrochemistry, and IR spectra. In addition, the UV spectra and the electrospray-ionization mass spectra (ESI-MS) were employed to investigated the stable pH value range of 1Co and 2Ni in aqueous solution.

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INTRODUCTION Polyoxometalates (POMs) are a kind of anionic clusters which contain early transition metal oxides in high state (e.g., Mo6+-, W6+-, V5+-, Nb5+-, Ta5+-oxides) that exhibit aesthetically fantastic topology and unique properties.1 Over the years, a large number of POMs have been reported and their intriguing properties (magnetism, electrochemistry, catalysis, etc.) endow them with potential application prospect and values in several fields, for example, environment, materials science, energy, health, and information technologies.2 Among the vast POMs family, the lacunary POMs are the most explored subset because the lacunary POMs can be regarded as good multidentate ligand-catching metal ions.3 Commonly, lacunary POMs are used as excellent precursors on account of the strengths as follows: (i) The lacunary POMs precursors are very easy to obtain from simple raw materials in high yield. (ii) Vacant sites are conducive to encapsulate various transition metals, including the mixed-valent metal ions. (iii) The robustness of POMs makes it possible to predict the frameworks of the ultimate products.4 Typical lacunary types usually contain {XW 9 O 34 }, {XW 10 O 36 }, {XW 11 O 39 }, {X2W12O48}, {X2W15O56}, and {X2W17O61}, (X = Si, P, As, Ge).5 Among them, the trivacant germanotungstate was first reported by Hervé et al. in 1977.6 Since then, a great deal of lacunary germanotungstate have been successively explored by Wang, Yang, Liu, and Kortz et al.7 In this regard, our group also reported a series of lacunary germanotungstate clusters [(OC)3Mn-(A-α-H2GeW9O34)]8−, [Cu(2,2′-bip y ) 2 ] 2 [ C u 6 ( 2 , 2 ′ - b i p y ) 2 ( G e W 9 O 3 4 ) 2 ] 4 − , an d [ C o (dap)2]2[Co4(Hdap)2(B-α-HGeW9O34)2]4−, among others.8 © XXXX American Chemical Society

Generally, the trivacant POMs units {XW9} (X = Si, Ge) did not easily to form the typical Dawson-type POMs, which may be due to the electrostatic repulsion of high-negative-charge {XO4} group. Thereby, the two trivacant Keggin units with {XO4} group are connected through two W−O−W bonds, giving rise to the germanotungstate based on open Wells− Dawson configuration.9a Moreover, the pocket between the two trivacant Keggin units can provide donor sites for accepting various kinds of metal cations. A lot of compounds have been successfully prepared by accommodating multiple metals (from one to six metals) in the open pocket, such as V5+, Mn2+, Fe3+, Tb3+, Eu, Ho3+, Dy3+, Gd3+, Co2+, Ni2+, Cu2+, Al3+, Ga3+, and Zn2+. For instance, the first open Wells− Dawson POMs [{K(H2O)3}2{K(H2O)2}(Si2W18O66)]13− was communicated by Hervé and coworkers in 2003.9b In 2004, Kortz’s group addressed a polyanion [Cu5(OH)4(H2O)2(A-αSiW9O33)2]10− which was the first polyoxotungstate substituted by five copper centers and quite fascinating for magnetic and electrocatalysis studies.9c In particular, Hill and co-workers reported a Ni5 cluster as catalyst for water oxidation, which largely drive the development of POMs with open Wells− Dawson configuration.9d In addition, the lanthanide (Ln)substituted polyoxotungstates based on open Wells−Dawson fragments [Ln2(H2O)7Si2W18O66]10− (Ln = Gd3+, Tb3+, Ho3+) were synthesized by Ni et al.9e It is noteworthy that all of the above examples were based on silicotungstate. In fact, the first germanotungstate based on open Wells−Dawson configuration Received: February 1, 2019

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DOI: 10.1021/acs.inorgchem.9b00315 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry [{Co(H2O)}(μ-H2O)2K(Ge2W18O66)]13− was successfully isolated by Liu’s group in 2006.9f The following year, this group addressed a class of germanotungstate [{M(H 2O)}(μH2O)2K{M(H2O)4}(Ge2W18O66)]11− (M = Co2+, Ni2+, Mn2+), and the pocket sites were occupied by two transition metals.9g As a continuation of the synthesis of novel germanotungstates with open Wells−Dawson structures, herein, we obtained two new germanotungstate K 1 0 H 1 0 {[Co(H2O)2]2[Co(H2O)3]2(Ge4W36O130)}·32H2O (1Co) and K 10 H 10 {[Ni(H 2 O) 2 ] 2 [Ni(H 2 O) 3 ] 2 (Ge 4 W 36 O 130 )}·32H 2 O (2Ni) which were synthesized by the reaction of the trivacant {GeW9} group and metal ions (Co2+ and Ni2+) in solution. The resulting compounds 1Co and 2Ni were characterized by single crystal X-ray diffraction crystallography and exhibit one type of new S-shaped polyanion, which represents the first instance of tetrameric germanotungstate with the open Wells− Dawson structure. As shown in Figure 1, the synthesis process

Figure 2. (a and b) Polyhedral/ball-and-stick representation of the of the polyanion of 1Co. (c and d) Coordination environment of Co1 and Co2 ion. Color code: WO6 octahedra, green black; W, green black; Ge, light blue; Co, purple; O, red. All the hydrogen atoms are not labeled to keep clarity.

connected via two W−O−W junctions or resulted from the Wells−Dawson structure through dividing four W−O−W junctions at the equator.9b A deep insight into the open Wells−Dawson structures POMs were given in Table S1. In comparison with the open Wells−Dawson structures based on silicotungstate, the utilization of Ge as hetero atoms is quite rare. Furthermore, the larger architectures in the field of open Wells−Dawson structure are infrequently discovered according to the literatures, most of which are two monomeric units of the open Wells−Dawson dimer. The double isomorphous open Wells−Dawson fragments of 1Co are formed by two {GeW9} units through a pair of W−O−W junctions (W9− O20−W14 and W8−O18−W15), respectively. As for the tetramer anion, there are two crystallographically equivalent pockets extant in the {Ge 4 W 36 } subunit, which can accommodate several cations: potassium, cobalt, or nickel. These cations are placed on each side of a {Ge2W18} subunit. For 1Co, the open pocket contains two pairs asymmetric sixcoordinate Co1 and Co2 centers, and both Co centers show a deformed octahedral configuration with the Co−O length ranging from 2.04(2) to 2.19(2) Å. There are also two pairs asymmetric six-coordinate Ni1 and Ni2 in the pocket of 2Ni (Figure S3). The bond lengths mostly align with those in other related Co-containing polytungstates.10 The Co1 atom is tied with two disconnected {GeW9} subsites via three μ2-O atoms (O5, O11, and O48 from two {GeW9} fragments, Co1−O5 = 2.04(2)Å, Co1−O11 = 2.08(3) Å, Co1−O48 = 2.11(2) Å), two O atoms from water ligands (O1W, O2W, Co1−O(H2O) = 2.08(2) Å−2.15(2) Å), and one μ4-O atom in the {GeW9} subunit which bridge two edge-sharing {WO6} octahedra (O46, Co1−O46 = 2.15(2) Å) (Figure 2c). The Co2 is surrounded by three μ2-O atoms (O13, O29 and O4, respectively from three corner-sharing {GeW9} fragments (Co2−O13 = 2.19(2) Å, Co2−O29 = 2.08(2) Å, Co2−O4 = 2.05(2) Å), and residual three O atoms from water molecules (O3W, O4W O5W, Co2−O(H2O) = 2.05(3)− 2.09(3) Å) (Figure 2d). The selected O−Co−O and O−Ni−

Figure 1. Representation of the assembly of structure {Ge4W36}. Color code: WO6 octahedra, green black; Ge, light blue; O, red. Hydrogen atoms are not labeled to keep clarity.

of the S-shaped germanotungstates are inferred from the structure. The resulting complexes can be synthesized through two steps: The first procedure is the constitution of dimeric species {Ge2W18} by two precursors {GeW9}, and then two {Ge2W18} subunits further combine to form the {Ge4W36} structure. From another perspective, the tetrameric polyanion can be assembled directly by four initial {GeW9} ion. Furthermore, the stabilities of 1Co and 2Ni in solution were investigated via Raman spectra, UV spectra, and the electrospray-ionization mass spectra (ESI-MS).

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RESULTS AND DISCUSSION Structural Description. Structural analysis indicates that 1Co and 2Ni are isomorphous and crystallize in the triclinic space group P1̅. Hence, the structure of 1Co was only described in detail here. 1Co is assembled of 1 tetramer Sshaped polyanion {Ge4W36O130}22−, 2 [Co(H2O)2]2+, 2 [Co(H2O)3]2+, 10 K+ counter cations, 32 lattice H2O molecules, and 10 H+ ions (Figure 2a,b). As shown in Figure S1, 2Ni consists of 1 polyanion {Ge4W36O130}22−, 2 [Ni(H2O)2]2+, 2 [Ni(H2O)3]2+, 10 K+ counter cations, 32 H2O molecules, and 10 H+ ions. The framework of S-shaped polyanion {Ge4W36} is comprised of two open Wells−Dawson structures bridged by two crystallographic equivalence W6−O16−W5 junctions (Figure S2). The open Wells−Dawson structures, as an interesting class of POMs family, are different from the typical Dawson-type POMs. The POMs with open Wells−Dawson configuration can be seemed as two trivacant Keggin subunits B


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Inorganic Chemistry

Raman bands at 958, 878, 825, and 663 cm−1 due to ν(W− Ot), ν(Ge−Oa), ν(W−Ob−W), and ν(W−Oc−W) vibrations, respectively (Figure S7). Both of which are consistent with the results of structural analysis. Furthermore, the Raman spectra in aqueous medium were conducted to identify the stability of 1Co and 2Ni in solution. The results shown that Raman spectra for 1Co and 2Ni in solid state and in aqueous solution are almost identical, which indicate the retention of these clusters that found in the solid state.12 The experimental XRD patterns of title compounds are consistent with the simulated XRD patterns which indicate the samples of 1Co and 2Ni are in good phase purity (Figure S8). Meanwhile, the crystal Raman spectra of 1Co and 2Ni both remains quite consistent with the bulk Raman spectra, which check again the purity of the samples (Figure S9). The UV spectra of 1Co and 2Ni were performed in aqueous solution. As shown in Figure S10, an inconspicuous absorption band appeared at 285 nm for 1Co and 283 nm for 2Ni, which are attributed to the pπ−dπ charge-transfer transitions of the Ob,c → W bonds. The obvious characteristic absorption bands at 196 nm for both 1Co and 2Ni due to the pπ−dπ chargetransfer transitions of the Ot → W bonds.13 Furthermore, the influences of time-dependent and pH value on the steadiness of chemical mixtures have been monitored by UV absorption spectra. The UV spectra of both compounds remained unchanged with different aging times (0−12 h) (Figure S10a,b), and they were stable in the pH value ranges of 2.5− 9.3 and 2.6−9.8, respectively (Figure S10c,d). Electrospray Ionization Mass Spectrometry (ESI-MS) Analysis. The ESI-MS is an efficient tool that affords a lot of reliable information in solution. Herein, the negative-ion ESIMS analysis was used to study liquid stability of 1Co and 2Ni in aqueous. The single crystals samples of 1Co and 2Ni were dissolved in deionized water. Figure S11, the negative mode of full scan mass spectra of the 1Co and 2Ni have been provided. The spectrum shows two dominant peaks for −7 and −6 charged ions, attributed to the intact cluster [K3H10Co4(H2O)7Ge4W36O130]7− and [K5H9Co4(H2O)9Ge4W36O130]6− of compound 1Co, respectively (Figure 4a). Prominent peaks that appear at m/z 1352.9991 (simulated 1352.9515) and 1597.4901 (simulated 1597.5179) clearly proves the stability of the complete anion group of 1Co in aqueous (Figure 4b and 4c). Meanwhile, the ESI-MS spectrum displays two prominent envelopes consistent with the complete group for 2Ni (Figure S12). These peaks were appointed to charge in −7 and −6 at m/z of 1360.8518 [K4H9Ni4(H2O)8Ge4W36O130]7− (simulated 1360.8041) and 1616.7910 [K 9 H 5 Ni 4 (H 2 O) 7 Ge 4 W 36 O 130 ] 6− (simulated 1616.7570), respectively (Figure S13). However, the intensity signal appeared at m/z = 1616.7910 is particularly weak, which indicates the fragment of [K9H5Ni4(H2O)7Ge4W36O130]6−is rare in the aqueous solutions of 2Ni. On account of the highly charged polyanion containing a good deal of atoms, hence these ESI-MS peaks are quite wide. It is difficult to identify the isotopic patterns.14 Furthermore, the influence of the pH values on structure for 1Co and 2Ni were studied. The self-buffering pH of aqueous solutions are about 6.64 and 6.70 for 1Co and 2Ni, respectively. Addition of HCl and NaOH could lead to the disintegration of polyanions in solution.15 In the pH range of 2.7−9.3, the dominant peaks of intact polyanion of 1Co were clearly observed (Figure 4d). The peaks assignable to the clusters slightly offset position and disappeared when the pH value was reduced above 2.7 by 1 M

O angles are summarized in Tables S2 and S3. The polyanions of 1Co and 2Ni somewhat resemble the structure of {KLiSi2W18O64(H2O)2}16− previously reported by Hervé and coworkes.9h However, there are also three obvious differences: (i) Hetero atoms of the former are the larger Ge atoms rather than Si, and the former is the first to report the tetramer germanotungstate polyanions with open Wells−Dawson structures. (ii) Transition metal cations Co2+ and Ni2+ are bounded into the {Ge4W36O130}22− tetramer anion, while only potassium atoms are filled into the pocket of the latter. (iii) The former was obtained from the self-assembly of lacunary precursor {GeW9} and M(NO3)2 (M = Co2+, Ni2+), whereas precursor of the latter was framework {Si2W18} with open Wells−Dawson structure. In addition, the tetramer polyanions {Ge4W36O130}22− of the two compounds can be extended into a 2D structure though K+ ions (Figure S4). All cobalt atoms and nickel both are confirmed to +2 according to bond valence sum (BVS) results (Tables S4 and S5). TGA, IR, XRD, Raman, and UV Characterization Studies. The thermogravimetric analysis (TGA) curves of 1Co and 2Ni exhibit one step of weight loss between 25−600 °C, giving a total loss of 8.60% (Cal. 8.86%) and 8.63% (Cal. 8.63%), which both may be assigned to forty-seven water molecules, respectively. (Figure S5). IR spectra of 1Co and 2Ni below 1000 cm−1 reveal the typical vibration absorptions of the Keggin-type polyanion. There are five vibration bands with 943; 881; 839, 784; and 716 cm−1 ascribed to ν(W−Ot), ν(Ge−Oa), ν(W−Ob−W), and ν(W−Oc−W) vibrations for 1Co, respectively. IR spectrum of 2Ni also displays the peaks at 940; 883; 849, 784; and 715 cm−1 associated with ν(W−Ot), ν(Ge−Oa), ν(W−Ob−W), and ν(W−Oc−W) (Figure S6).11 Compared to the IR spectrum of K8Na2[A-α-GeW9O34]·25H2O, the ν(W−Ot) vibration peak for 1Co and 2Ni both have a bathochromic shift, the potential cause of which is possibly that cations Co2+ or Ni2+ maintain stronger interactions with the terminal oxygen atoms of the polyanion. The Raman spectra in the solid state were carried out as a supplement to the IR test results. As shown in Figure 3, the obvious characteristic Raman bands at 957 and 889 cm−1 are attributable to ν(W−Ot) and ν(Ge−Oa) vibrations for 1Co, and the indistinct characteristic Raman bands at 768 and 669 cm−1 are assigned to ν(W−Ob−W) and ν(W−Oc−W) vibrations. For compound 2Ni, there are four characteristic

Figure 3. Raman spectra of 1Co in aqueous solution (back) and in solid state (red). C


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Inorganic Chemistry

potential region of 2Ni, which are also coincided with the redox processes of WVI (Figure 5a). However, no electro-

Figure 4. (a) ESI-MS spectra vesting in the complete polyanion for 1Co.(b and c) Artificial (blue) and experimental (black) stay at near m/z 1352.9991 and 1597.4901. (d) ESI-MS of 1Co in the process of titration in various pH’s in the range of m/z = 1250−1700. Figure 5. (a) CV curves of 2Ni at different scan rates. (b) Difference of the peak currents degree for 2Ni is in proportion to the square root graph of the scan rates from 25 to 400 mV/s. (Color code: red: anodic, black: cathodic).

HCl, indicating that the structure of 1Co may be destroyed. The intensity of peaks of intact 1Co polyanion decreases with increasing the pH value above 9.3 by 2 M NaOH, which proves the decomposition of the cluster. Hence, a conclusion was drawn that the intact polyanion of 1Co kept steady in a broad range pH value (2.7−9.3) in aqueous solutions. As well, the cluster of 2Ni is still stable in a wide pH value region of 2.6−9.8 (Figure S14). When titrating with 1 M HCl, peak intensity assignable to the clusters [K4H9Ni4(H2O)8Ge4W36O130]7− significantly decreases in abundance at pH < 2.6. ESI-MS spectra during a base titration of 2Ni also have proved the decomposition of the cluster at pH > 9.8. Therefore, the ESI-MS spectra and the UV spectra both demonstrate the stability of 1Co and 2Ni in the wide pH value range of aqueous solution. Electrochemical Studies. The electrochemical behaviors of 1Co and 2Ni are observed in pH 5.0 (0.5 M, Na2SO4) solution. Cyclic voltammetry (CVs) have the same general shapes in the potential region from +1.2 to −1.2 V for 1Co and 2Ni. As shown in Figure S15, two reduction waves (−0.545 V, −0.946 V) and two oxidation potentials (−1.012 V, −0.677 V) were observed in the negative potential region of 1Co, which may belong to the redox processes based on WVI atoms.16 However, only one additional oxidation peak −0.669 V and two redox waves at −0.549 and −0.987 V was observed in the

chemical activity has been detected in the potential domains explored for CoII and NiII. Moreover, the effect of the scanning rates of 1Co and 2Ni has also been studied under the same solution condition. Figures S16 and 5b show that the peak currents stay in proportion to the square root of the scan rates while the scanning rate is increased from 25 to 400 mV/s, yet the mean peak potential tend to not shift evidently. It suggests that the redox processes are possibly surface-controlled electron-transfer in a detailed scope of scan rates.17

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CONCLUSION In summary, two tetrameric germanotungstates with open Wells−Dawson structures, K 10 H 10 {[Co(H 2 O) 2 ] 2 [Co(H2O)3]2(Ge4W36O130)}·32H2O (1Co) and K10H10{[Ni(H2O)2]2[Ni(H2O)3]2(Ge4W36O130)}·32H2O (2Ni), have been successfully constructed through a conventional aqueous method and structurally characterized. The polyanions of 1Co and 2Ni show the S-shaped tetrameric structure, and the open pocket accommodates cobalt or nickel. The study of electrochemical indicate the redox processes of the WVI in D


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Inorganic Chemistry

established by TGA analysis. No hydrogen atoms associated with the water molecules got its position from Fourier map. All H atoms on water molecules were straightly incorporated in the structural formula. A conclusion of the crystal information and structure refinements are summarized in the following Table 1.

compound 1Co and 2Ni. Simultaneously, the Raman spectra for 1Co and 2Ni in solid state and in aqueous solution both are almost identical, which indicate the stability of 1Co and 2Ni in solution. Furthermore, the negative-ion ESI-MS spectra and the UV spectra demonstrate that 1Co and 2Ni were steady in the wide pH value ranges of 2.7−9.3 and 2.6−9.8, respectively, suggesting a robust use in applications.

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Table 1. Crystallographic Data Parameters for 1Co and 2Ni

EXPERIMENTAL SECTION

empirical formula formula weight temperature (K) crystal system space group a [Å] b [Å] c [Å] α [°] β [°] γ [°] V [Å3] Z ρcalcd [g cm−3] μ [mm−1] F (000) index ranges

Material and Physical Measurements. The TGA curves were performed under flowing N2 atmosphere using a Mettler−Toledo TGA/SDTA 851e heat analysis meter with a heating ratio of 10 °C min−1 from 25 to 600 °C. IR spectra were carried out on a BrukerVertex 70 FT-IR spectrometer using KBr pellets under the scope of 4000−450 cm−1. XRD data were obtained on a Bruker AXS D8 Advance diffraction meter with Cu Kα radiation (λ = 1.5418 Å) at 293 K. Raman spectra were performed on a Renishaw inVia with a red Spectra-Physics He−Ne laser (wavelength of 633 nm and 500 mW capacity). The UV−vis absorption spectra were gain with a U-4100 spectrometer. Inductively coupled plasma (ICP) results were gained on a PerkinElmer Optima 2000 ICP-OES spectrometer. Electrochemical curves were recorded using a CHI660E electrochemical working station. A traditional three-electrode mechanism was employed, and glassy carbon, platinum wire, and saturated calomel were used as working electrode, counter electrode, and reference electrode (SCE), respectively. The ESI-MS spectrum measurements were recorded using a Q EXACTIVE mass spectrometry in the negative ion mode and the data were analyzed by the Peak view 2.0 software. Synthesis of 1Co and 2Ni. The overall chemicals were applied as bought without being made pure. The lacunary precursor K8Na2[A-αGeW9O34]·25H2O was produed by hydrolysis of K6Na2[GeW11O39]· 13H2O, and its pure state was proved by IR spectroscopy.18 Synthesis of 1Co, K10H10{[Co(H2O)2]2[Co(H2O)3]2(Ge4W36O130)}· 32H2O. A 0.025 g (0.83 mmol) sample of NaNO3 was dissolved in 15 mL of distilled water under stirring, followed by the addition of 1.33 g (0.33 mmol) of K8Na2[A-α-GeW9O34]·25H2O and 0.39 g (1.33 mmol) of Co(NO3)2. Subsequently, HCl (1 mL, 1M) was put into the mixture, and the mixture was stirred for 30 min. The emulsion was filtered, and KCl solution (2.5 mL, 1M) was put into the filtrate. The solvent was mechanically stirred at 60 °C for 3 h. The red solution was got after the second filtration and to be cold to the room temperature. Slow evaporation of the filtrate yielded red crystals of 1Co after 4 weeks (yield: ca. 18% on the basis of Co(NO3)2). ICP: Anal. Calcd (found) %: Co 2.646 (2.22), Ge 2.72 (2.69), K 3.579 (3.62), W 59.095 (61.3). IR (KBr pellet): 3254(br), 1633(s), 1423(s), 943(s), 881(w), 839(m), 784(w), 716(s), 548(s) cm−1. Raman (cm−1): 957(s), 889(m), 768(w), 669(w). Synthesis of 2Ni, K10H10{[Ni(H2O)2]2[Ni(H2O)3]2(Ge4W36O130)}· 32H2O. The synthesis of 2Ni was similar to 1Co except that Co(NO3)2 (0.39 g, 1.33 mmol) was replaced by Ni(NO3)2 (0.27 g, 1.33 mmol). Finally, green block-shaped crystals of 2Ni were afforded after approximately 4 weeks (yield: ca. 15% based on Ni(NO3)2). ICP: Anal. Calcd (found) %: Ni 2.658 (2.22), Ge 2.80 (2.75), K 3.63 (3.70), W 60.08 (62.66). IR (KBr pellet): 3417(br), 1635(s), 1394(s), 940(s), 883(w), 849(m), 784(w), 715(s), 545(s) cm−1. Raman (cm−1): 958(s), 878(m), 825(w), 663(w). X-ray Crystallography. The suitable sample of 1Co and 2Ni were sealed in a glass tube and the information about X-ray diffraction degree were performed on a Bruker APEX-II CCD diffraction meter with the graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 296(2) K. Lorentz and polarization rectification were utilized, and an applied multiscan assimilation rectification was achieved with the SADABS scheme.19 Using Olex2, the frameworks of 1Co and 2Ni were detected by immediate ways (SHELXS-97) and Fourier syntheses improved with the SHELXL refinement package applying least-squares minimization algorithm. In the last step, the nonhydrogen atoms there were refined anisotropically. The part of lattice water molecules were positioned by Fourier map, and the rest were

reflections collected independent reflections data/restraints/ parameters goodness-of-fit on F2 R1, wR2 [I > 2σ(I)] largest diff. peak/hole (e Å−3)

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1Co

2Ni

H94Co4Ge4K10O172W36 10382.16 296.15 triclinic P1̅ 14.4265 (19) 17.022 (2) 21.010 (3) 70.805 (2) 78.291 (2) 72.317 (2) 4611.6 (11) 1 3.578 23.648 4290.0 −16 ≤ h ≤ 17 −15 ≤ k ≤ 20 −22 ≤ l ≤ 25 23980 16338 [Rint = 0.0623]

H94Ni4Ge4K10O172W36 10381.20 296.15 triclinic P1̅ 14.4028 (10) 17.0350 (3) 20.8888 (3) 70.6140 (10) 78.1080 (10) 72.2800 (10) 4573.58 (13) 1 3.654 23.899 4358.0 −17 ≤ h ≤ 17 −20 ≤ k ≤ 20 −24 ≤ l ≤ 24 57170 16243 [Rint = 0.0527]

16338/0/543

16243/0/559

1.010 0.0733, 0.1916 4.44/−3.97

1.085 0.0481, 0.1677 4.49/−4.43

ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b00315. Polyhedral and ball-and-stick and the coordination environment of 2Ni; TGA, IR, XRD, Raman, and UV−vis spectra; ESI-MS spectrum and CV curves (PDF) Accession Codes

CCDC 1867816 and 1867817 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

*E-mail: [email protected] (J.-Y.N.). *E-mail: [email protected] (J.-P.W.). ORCID

Jingyang Niu: 0000-0001-6526-7767 E


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Inorganic Chemistry Notes

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The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Nature Science Foundation of China (21771053, 21771054, 21571050, 21573056) and the Natural Science Foundation of Henan Province (132300410144 and 162300410015).

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