Linking 1D Transition-Metal Coordination Polymers and Different

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

Linking 1D Transition-Metal Coordination Polymers and Different Inorganic Boron Oxides To Construct a Series of 3D Inorganic− Organic Hybrid Borates Shao-Chen Zhi,† Yue-Lin Wang,† Li Sun,† Jian-Wen Cheng,*,‡ and Guo-Yu Yang*,† †

MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China ‡ College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua, Zhejiang 321004, China S Supporting Information *

ABSTRACT: Three inorganic−organic hybrid borates, M(1,4-dab)[B5O7(OH)3] [M = Zn (1), Cd (2), 1,4-dab = 1,4-diaminobutane)] and Co(1,3-dap)[B4O7] (3, 1,3-dap = 1,3-diaminopropane), which integrated characteristics of 1D coordination polymers and 1D/3D inorganic boron oxides have been obtained under solvothermal conditions. Compounds 1 and 2 are isostructural and crystallize in a centrosymmetric space group P21/c; the 3D achiral structures of 1 and 2 consist of the nonhelical Zn/Cd-1,4-dap coordination polymers and 1D B−O chains. Compound 3 crystallizes in a chiral space group P43212; the helical Co-1,3-dap coordination polymer chains are entrained within a 3D B−O network and finally form the chiral framework. Compounds 1−3 represent good examples of using coordination polymers to construct mixed-motif inorganic−organic hybrid borates. Compounds 1 and 2 display blue luminescence when excited with UV light.

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INTRODUCTION Crystalline inorganic borates are promising solid state materials for their diverse structural types and wide applications.1−5 BO3 triangles (Δ) and BO4 tetrahedra (T) easily form various cluster building units with different shapes and sizes.6−8 A notable example is nanosized [B69O108(OH)18] cluster,6 which is constructed from two smaller B5O12 and B9O16(OH)3 units, and represents the largest cluster sizes in reported borates. By sharing corners/edges, these cluster building units can further polymerize into chains, layers, and 3D networks.9−12 For example, the Yang group obtained three inorganic borates with 4-connected qtz net, 6-connected pcu net, and 4,6-connected binodal net, in which B3O7 and B6O13 units act as 4- and 6connected nodes, respectively.9 Due to their unique structural features and wide UV transmittance, borates are among the best candidates for UV/deep-UV nonlinear optical (NLO) materials, among which LBO (LiB3O5), BBO (β-BaB2O4), and KBBF (KBe2BO3F2) are the most remarkable examples.13−15 It is believed that distorted planar borate rings are responsible for the second harmonic generation (SHG) response via anionic group theory. Coordination polymers are another important group of crystalline solids based on the linkage of organic ligands and metal ions.16 The designed organic ligands and selected coordination geometries of metal ions make this type of structure more likely to be predicted. Over the past decades, a large number of coordination polymers with different dimensions have been made; they exhibit potential applications © XXXX American Chemical Society

in gas storage and separation, magnetism, and luminescence.17,18 The incorporation of coordination polymers and inorganic backbones into the same framework leads to new types of mixed-motif crystalline solids, inorganic−organic hybrid solids. For example, the Zubieta and Yang groups reported a series of mixed-motif non-interpenetrating inorganic−organic hybrid solids, in which different inorganic 1D molybdenum oxide/ copper halide chains connect with various 1D, 2D, and 3D coordination polymers.19,20 In these compounds, two different metal ions usually maintain their own structural motifs due to their unique coordination preferences. To date, isolated transition-metal complexes usually act as templates in the synthesis of open-framework borates.21 However, borate frameworks contain mixed-motifs of coordination polymers and B−O units are rare. Recently, we reported a novel aluminoborate (ABO), [Zn(dap)2][AlB5O10] (dap = 1,3-diaminopropane), which contains mixed-motif interpenetrating networks of a 3D ABO with dia net and a 2D Zn-dap coordination polymer with sqltype net.22 If other types of coordination polymers incorporate into the various inorganic B−O networks in an interpenetrating/non-interpenetrating way, new types of inorganic−organic hybrid borates would be expected. In this study, we obtain three B−O−transition-metal−organic frameReceived: October 28, 2017

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DOI: 10.1021/acs.inorgchem.7b02765 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry works: M(1,4-dab)[B5O7(OH)3] [M= Zn (1), Cd (2), 1,4-dab = 1,4-diaminobutane)] and Co(1,3-dap)[B4O7] (3, 1,3-dap = 1,3-diaminopropane), via solvothermal reactions of H3BO3, Zn(OH)2/Cd(OH)2/Co(OH)2, and 1,4-dab/1,3-dap in pyridine and ethanol at 190 °C for 9 days. Compounds 1−3 contain mixed-motif non-interpenetrating 1D transition metal coordination polymers and 1D/3D inorganic boron oxides.

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Table 1. Crystal Data and Structure Refinement for 1−3

FW cryst syst space group λ/Å a/Å b/Å c/Å β/deg V/Å3 Z Dcalcd /g cm−3 μ/mm−1 F(000) GOF R1, wR2 [I > 2σ(I)]a R1, wR2 (all data) peak and hole (e/Å−3)

EXPERIMENTAL SECTION

Materials and Methods. All the chemicals were obtained from commerce and used without further purification. The IR spectra (KBr pellets) were recorded on a Thermo Scientific Nicolet iS10 FT-IR spectrometer in the range 400−4000 cm−1. Elemental analyses were performed on a EuroEA3000 elemental analyzer. Thermogravimetric analyses were performed on a Mettler Toledo TGA/DSC 1100 analyzer from room temperature to 1000 °C in air atmosphere. Powder X-ray diffraction (PXRD) data were collected by a Bruker D8 Advance XRD diffractometer using Cu Kα radiation (λ = 1.540598 Å). The UV−vis spectra were recorded on a Shimadzu UV-3600 spectrometer equipped with an integrating sphere in the range 190− 800 nm (BaSO4 plate as a standard). The photoluminescence spectra were recorded on an Edinburgh Instruments FLS-980 spectrometer at room temperature. The solid-state circular dichroism (CD) spectrum was recorded on a Jasco J-810 circular dichroism spectropolarimeter. Synthesis of Compounds 1−3. Compound 1 was obtained under solvothermal conditions. A mixture of H3BO3 (8 mmol) and Zn(OH)2 (1 mmol) was added to the mixture of pyridine (2 mL) and ethanol (2 mL). Then 1,4-dah (1 mL) was slowly added with constant stirring for about 1 h. The emulsion was sealed in a 25 mL Teflonlined stainless-steel autoclave and then heated at 190 °C for 9 days. After cooling to room temperature, colorless block crystals of 1 (47% yield based on Zn) were obtained. Anal. Calcd (%) for C4N2H15B5ZnO10 (1): C 12.96, N 7.56, H 4.04. Found: C 12.72, N 7.41, H 4.15. Compound 2 was obtained by a similar procedure as for 1, except that Zn(OH)2 was replaced by Cd(OH)2 (1 mmol) (yield 51% based on Cd). Anal. Calcd (%) for C4N2H15B5CdO10 (2): C 11.50, N 6.71, H 3.59. Found: C 11.24, N 6.57, H 3.77. Purple octahedral crystals of 3 were obtained by a similar procedure as for 1 except that Zn(OH)2/1,4-dab was replaced by Co(OH)2/1,3dap (1 mmol/1 mL) (42% yield based on Co). Anal. Calcd (%) for C3N2H10B4CoO7 (3): C 12.50, N 9.72, H 3.47. Found: C 12.33, N 9.62, H 3.56. The experimental powder X-ray diffraction (PXRD) peaks of the three compounds are in accordance with the simulated PXRD peaks, indicating the purity of the three compounds (Figure S1). Structural Determination. The intensity data of 1 and 2 were collected on a Gemini A Ultra CCD with graphite-monochromated Cu Kα radiation (λ = 1.540598 Å), while those for compound 3 were collected with Mo Kα radiation (λ = 0.71073 Å) at 293(2) K. All absorption corrections were performed using the multiscan program. Both structures were solved by direct methods and refined by a fullmatrix least-squares fitting on F2 using the SHELXTL-2014 program.23 In the structures, anisotropic displacement parameters were refined for all non-hydrogen atomic sites, and the hydrogen atoms were geometrically placed and refined using a riding model. The ADDYSM algorithm from the program PLATON was used for verifying the structures,24 and no higher symmetry was found. Crystallographic data and structure refinement information are summarized in Table 1. CCDC 1557130 (1), 1557131 (2), and 1557132 (3) contain the supplementary crystallographic data for this paper.

C4N2H15B5ZnO10 (1)

C4N2H15B5CdO10 (2)

C3N2H10B4CoO7 (3)

370.61 monoclinic P21/c 1.54178 9.8663(2) 8.8985(2) 16.5278(4) 116.285(2) 1301.03(5) 4 1.892 3.152 752 1.105 0.0282, 0.0723

417.64 monoclinic P21/c 1.54178 9.9235(4) 8.9206(4) 16.8006(9) 115.493(4) 1342.45(12) 4 2.066 13.546 824 1.081 0.0349, 0.0825

288.3 tetragonal P43212 0.71073 8.5818(3) 8.5818(3) 12.6324(9) 90 930.34(9) 4 2.058 1.868 580 1.044 0.0328,0.0775

0.0304, 0.0737

0.0468,0.0895

0.0400,0.0813

0.585/−0.670

0.948/−0.934

0.308/−0.359

R1 = ∑∥Fo| − |Fc∥/∑|Fo|, wR2 = {∑w[(Fo)2 − (Fc)2]2/ ∑w[(Fo)2]2}1/2.

a

of 1,4-dab molecules are found in the asymmetric unit (Figure 1a). The inorganic part of 1 is an infinite 1D B−O chain along

Figure 1. (a) Asymmetric unit of 1. Symmetry codes: (i) 1 − x, −y, 1 − z; (ii) 1 − x, 1 − y, −z; (iii) 1.5 − x, 0.5 + y, 0.5 − z. (b) The B5O8(OH)3 cluster in 1.

the b-axis, which contains an unusual fundamental building block of B5O8(OH)3 (Figures 1b, 2a). According to the classification scheme of Christ and Clark, the B5O8(OH)3 unit can be described as 5:[4:(2Δ+2T)+Δ]. Generally, pentaborate units usually contain two perpendicular B3O3 rings,25 while the B5O8(OH)3 unit differs from such configuration and consists of a B4O8(OH) unit and an attached BO(OH)2 group. The B−O bond lengths vary from 1.347(3) Å to 1.504(2) Å (Table S1). The O−B−O angles are in the ranges 117.2(2)−123.1(2)° for BO3 triangles and 105.2(2).1−115.0(2)° for BO4 tetrahedra, respectively. These values are all in good agreement with other borates in previous reports. The other motif in 1 is a 1D Zn-1,4-dab coordination polymer along the c-axis (Figure 2b). The crystallographically independent Zn2+ ion is five-coordinated in a distorted trigonal bipyramidal configuration: two N and three O atoms from two different 1,4-dab and B−O units, respectively. The Zn−N/O bond lengths are in the region of 2.0262(13)−2.2567(13) Å. This 1D coordination polymer interconnected with the inorganic chain into the final 3D framework (Figure 2c). Extensive H bonds are observed due to the organic amines and terminal hydroxyl groups in the structure (Figure S2, Table S2).

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RESULTS AND DISCUSSION Structures of M(1,4-dab)[B5O7(OH)3] [M = Zn (1), Cd (2)]. We describe the structure of 1 as an example because 1 and 2 are isostructural. Compound 1 crystallizes in the centrosymmetric monoclinic space group P21/c. Twenty-two non-hydrogen atoms, including 1 Zn, 5 B, 10 O, and two halves B

DOI: 10.1021/acs.inorgchem.7b02765 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 2. (a) Polyhedral view of 1D B−O chain. (b) 1D Zn-1,4-dab coordination polymer. (c) View of 3D framework of 1 along the b-axis.

Due to the larger ionic radius of Cd2+ in 2, Cd2+ adopted the six-coordinated distorted octahedral geometry; the Cd−N/O bond lengths vary from 2.241(4) to 2.686(3) Å (Table S3, Figure S3). Structure of Co(1,3-dap)[B4O7] (3). Compound 3 crystallizes in the tetragonal chiral space group P43212. There are 10 independent non-hydrogen atoms in the asymmetric unit of 3, including 0.5, 2 B, 3.5 O, and 0.5 1,3-dap (Figure 3a).

Figure 4. (a) Polyhedral view of 3D B−O network. (b) 1D L-helical Co-1,3-dap chain. (c) View 3D framework of 3 along the c-axis.

Co−O and Co−N distances range from 1.945(3) to 2.252(3) Å. This trigonal-bipyramidal coordination of Co2+ ion is first observed in the cobalt borate family. The linkage between Co2+ and 1,3-dap gives a motif of L-helical Co-1,3-dap chain along the c-axis (Figure 4b). The helical chains are located in the pores and connect with the walls of inorganic B−O network (Figure 4c). Recently, an isostructural borate with Zn-1,3-dap chain was reported.26 In a previously reported inorganic cobalt borate Na2Co2B12O21, the edge-shared octahedral Co2+ dimers are found in the small channels.27 Compounds 1−3 contain 1D coordination polymers and 1D/3D inorganic boron oxides. Previously, Natarajan and coworkers reported several similar inorganic−organic hybrid borates, which consist of 1D coordination polymers and 1D/ 2D inorganic boron oxides.28 The coordination polymers are important to the final structures of borates (Table S6). In compounds 1 and 2, nonhelical Zn/Cd-1,4-dap coordination polymers and 1D B−O chains lead to the final achiral structures. While in compound 3, the L-helical Co-1,3-dap chains may transfer the configuration and symmetry

Figure 3. (a) Asymmetric unit of 3. Symmetry codes: (i) y, x, −1 − z; (ii) 0.5 − y, 0.5 + x, −0.25 + z; (iii) y, x, −z; (iv) −y, −x, −0.5 − z; (v) −x, −y, −0.5 + z; (vi) −0.5 + y, 0.5 − x, 0.25 + z. (b) The B4O9 cluster in 3.

B1 and B2 are 4- and 3-fold coordinated with O atoms forming BO4 tetrahedra and BO3 triangles, respectively. B−O distances vary from 1.356(5) to 1.482(4) Å (Table S5), and O−B−O angles vary from 104.8(3) to 121.8(3)°. These values are similar to those for compound 1. The inorganic motif in 3 is a 3D open-framework B−O network constructed from B4O9 units (Figures 3b, 4a). Each B4O9 unit connects with four B4O9 units by corner-sharing O atoms, and gives rise to a diamond net with multidimensional channels running along three different directions. The Co2+ ion exhibits a trigonal-bipyramidal coordination geometry: three oxygen atoms from three B4O9 clusters and two nitrogen atoms from two different 1,3-dap ligands; the C

DOI: 10.1021/acs.inorgchem.7b02765 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry information into the inorganic B−O network, and finally form the chiral framework (Figure 5). The solid-state circular

be attributed to the weak d−d transition of Co2+ ions (Figure 7).

Figure 5. Linkage between L-helical Co-1,3-dap chain and the helical B−O backbone in 3. Figure 7. Optical diffuse reflectance spectra of 1−3.

dichroism (CD) spectrum indicates that compound 3 is homochiral and may be racemic (Figure S6). Compared with 1,4-dab in 1 and 2, the shorter length of the 1,3-dap in 3 led to the shorter distance between the adjacent terminal B−OH groups, and polymerized into a high-dimensional borate framework (Figure 6).

Compounds 1 and 2 display blue luminescence with maximum fluorescent emission at 412 and 423 nm when excited at 384 and 356 nm, respectively (Figure 8a). The

Figure 8. (a) Emission spectra of 1 and 2. (b) The luminescence decay curves of 1 and 2.

lifetime for the maximum emission bands of 1 and 2 is 4.09 and 4.67 ns (Figure 8b), respectively. Similar luminescences have been observed in other Zn2+/Cd2+ inorganic−organic hybrid borates22,29 and organically templated borates (nonmetal).30 The emission spectra of these nonmetal borates are suggested from borate framework rather than the organic amines.30 In addition, Zn/Cd metal−organic frameworks usually show similar luminescences for LMCT (ligand-to-metal charge transfer).31 The blue luminescence of 1 and 2 may be due to the borate framework and/or LMCT, since there are both Zn/ Cd coordination polymers and inorganic boron oxides in the structures of 1 and 2. When excited under UV light, compound 3 shows no luminescence emission, which may be due to the quenching of the fluorescence by Co2+ ions,32 because isostructural zinc borate shows an emission peak at 385 nm when excited at 256 nm.26

Figure 6. Connection between 1D transition-metal coordination polymers and inorganic boron oxides in 1 (a) and 3 (b).

Optical Properties. Optical diffuse reflectance studies reveal that the band gaps of 1−3 are about 4.6, 5.9, and 3.9 eV, respectively. The values of 1 and 2 are comparable with that of [Zn(dap)2][AlB5O10] (5.82 eV).22 The spectrum of 3 shows a weak absorption peak at 540 nm (corresponding with 2.2 eV) corresponding to the purple crystals of compound 3, which can D

DOI: 10.1021/acs.inorgchem.7b02765 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

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Evaluation of f-element Borate Chemistry. Coord. Chem. Rev. 2016, 323, 36−51. (5) (a) Tian, H.; Wang, W.; Gao, Y.; Deng, T.; Wang, J.; Feng, Y.; Cheng, J. Facile Assembly of an Unusual Lead Borate with Different Cluster Building Units via a Hydrothermal Process. Inorg. Chem. 2013, 52, 6242−6244. (b) Song, J.; Hu, C.; Xu, X.; Kong, F.; Mao, J. A Facile Synthetic Route to a New SHG Material with Two Types of Parallel pConjugated Planar Triangular Units. Angew. Chem., Int. Ed. 2015, 54, 3679−3682. (c) Pan, R.; Cheng, J.; Yang, B.; Yang, G. CsBxGe6−xO12 (x = 1): A Zeolite Sodalite-Type Borogermanate with a High Ge/B Ratio by Partial Boron Substitution. Inorg. Chem. 2017, 56, 2371− 2374. (d) Yu, S.; Gu, X.; Deng, T.; Huang, J.; Cheng, J.; Yang, G. Centrosymmetric (Hdima)2[Ge5B3O15(OH)] and Noncentrosymmetric Na4Ga3B4O12(OH): Solvothermal/ Surfactant-Thermal Synthesis of Open-Framework Borogermanate and Galloborate. Inorg. Chem. 2017, 56, 12695−12698. (6) Wang, J.; Yang, G. A Novel Supramolecular Magnesoborate Framework with Snowflake-Like Channels Built by Unprecedented Huge B69 Cluster Cages. Chem. Commun. 2017, 53, 10398−10401. (7) Mutailipu, M.; Zhang, M.; Su, X.; Yang, Z.; Pan, S. Na8MB21O36 (M = Rb and Cs): Noncentrosymmetric Borates with Unprecedented [B21O36]9‑ Fundamental Building Blocks. Inorg. Chem. 2017, 56, 5506−5509. (8) Yao, W.; Jiang, X.; Huang, H.; Xu, T.; Wang, X.; Lin, Z.; Chen, C. Sr8MgB18O36: a New Alkaline-Earth Borate with a Novel ZeroDimensional (B18O36)18− Anion Ring. Inorg. Chem. 2013, 52, 8291− 8293. (9) (a) Wang, J.; Cheng, J.; Wei, Q.; He, H.; Yang, B.; Yang, G. NaB3O5·0.5H2O and NH4NaB6O10: Two Cluster Open Frameworks with Chiral Quartz and Achiral Primitive Cubic Nets Constructed from Oxo Boron Cluster Building Units. Eur. J. Inorg. Chem. 2014, 2014, 4079−4083. (b) Wang, E.; Huang, J.; Yu, S.; Lan, Y.; Cheng, J.; Yang, G. An Ultraviolet Nonlinear Optic Borate with 13-Ring Channels Constructed from Different Building Units. Inorg. Chem. 2017, 56, 6780−6783. (10) Abudoureheman, M.; Han, S.; Wang, Y.; Liu, Q.; Yang, Z.; Pan, S. Three Mixed-Alkaline Borates: Na2M2B20O32 (M = Rb, Cs) with Two Interpenetrating Three-Dimensional B-O Networks and Li4Cs4B40O64 with Fundamental Building Block B40O77. Inorg. Chem. 2017, 56, 13456−13463. (11) (a) Lin, Z.; Yang, G. Oxo Boron Clusters and Their Open Frameworks. Eur. J. Inorg. Chem. 2011, 2011, 3857−3867. (b) Belokoneva, E. L.; Dimitrova, O. V. Acentric Polyborate, Li3[B8O12(OH)3], with a New Type of Anionic Layer and Li Atoms in the Cavities. Inorg. Chem. 2013, 52, 3724−3727. (12) (a) Wei, Q.; Wang, J.; He, C.; Cheng, J.; Yang, G. DeepUltraviolet Nonlinear Optics in a Borate Framework with 21-Ring Channels. Chem. - Eur. J. 2016, 22, 10759−10762. (b) Wang, J.; Wei, Q.; Cheng, J.; He, H.; Yang, B.; Yang, G. Na2B10O17·H2en: A Threedimensional Open-framework Layered Borate Co-templated by Inorganic Cations and Organic Amines. Chem. Commun. 2015, 51, 5066−5068. (13) Chen, C.; Wu, Y.; Jiang, A.; Wu, B.; You, G.; Li, R.; Lin, S. New Nonlinear-Optical Crystal: LiB3O5. J. Opt. Soc. Am. B 1989, 6, 616− 621. (14) Chen, C.; Wu, B.; Jiang, A.; You, G. A New-Type Ultraviolet SHG Crystal β-BaB2O4. Sci. Sin. Ser. B 1985, 28, 235−243. (15) Mei, L.; Wang, Y.; Chen, C.; Wu, B. Nonlinear Optical Materials Based on MBe2BO3F2 (M = Na, K). J. Appl. Phys. 1993, 74, 7014− 7015. (16) Férey, G. Hybrid Porous Solids: Past, Present, Future. Chem. Soc. Rev. 2008, 37, 191−214. (17) Morris, R. E.; Bu, X. Induction of Chiral Porous Solids Containing Only Achiral Building Blocks. Nat. Chem. 2010, 2, 353− 361. (18) Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Introduction to MetalOrganic Frameworks. Chem. Rev. 2012, 112, 673−674. (19) (a) Hagrman, D.; Zubieta, C.; Rose, D. J.; Zubieta, J.; Haushalter, R. C. Composite Solids Constructed From One-

CONCLUSION In summary, we synthesized three new inorganic−organic hybrid transition-metal borates under solvothermal conditions. These compounds contain two distinct non-interpenetrating motifs; the nonhelical/helical metal−organic coordination polymer chains connect with 1D/3D boron oxides and lead to 3D achiral/chiral structures. The coordination polymers are important to the final structures of borates. Compounds 1 and 2 show blue luminescence. This work offers an effective way to expand the family of borates by changing the coordination polymer parts using different ligands, and further modify the inorganic−organic hybrid frameworks.

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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.7b02765. Selected bond distances, PXRD patterns, IR spectra, TGA, solid-state CD spectra, and additional structures (PDF) Accession Codes

CCDC 1557130−1557132 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]. *E-mail: [email protected]. ORCID

Jian-Wen Cheng: 0000-0002-7571-0096 Guo-Yu Yang: 0000-0002-0911-2805 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the NSFC (21571016, 91122028) and the NSFC for Distinguished Young Scholars (20725101).

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REFERENCES

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DOI: 10.1021/acs.inorgchem.7b02765 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

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DOI: 10.1021/acs.inorgchem.7b02765 Inorg. Chem. XXXX, XXX, XXX−XXX