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Synthesis and Characterization of a Terpyridine Ligand and Its Interactions with Selected Metal Ions

Meng YU ,  Jian-Mei HU ,  Yong WANG

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Citation:  Meng YU, Jian-Mei HU, Yong WANG. Synthesis and Characterization of a Terpyridine Ligand and Its Interactions with Selected Metal Ions[J]. Chinese Journal of Structural Chemistry, 2020, 39(4): 783-792. doi: 10.14102/j.cnki.0254-5861.2011-2498 shu

Synthesis and Characterization of a Terpyridine Ligand and Its Interactions with Selected Metal Ions

English

  • 1. INTRODUCTION

    2,2΄:6΄,2΄΄-Terpyridines (tpys) are one of the largely utilized N-heterocycle ligands in coordination chemistry for energy conversion systems because they generally form stable complexes with a well-defined structure[1, 2]. They have very high binding affinity toward transition metal ions owing to strong dπ-pπ* back bonding and the chelate effect. Due to their excellent charge-transfer properties and/or intriguing luminescence properties, terpyridine-based coordination compounds have potential applications in optics and electronics[3-5]. A metalligand charge transfer takes place in the electronic absorption and emission spectra of the terpyridinebased complexes, which can be used to select and identify various metal ions[6-8]. Furthermore, these ligands can be used for the construction of geometrically well-defined functional complexes which show fascinating properties based on intra/intermolecular electron and energy transfer. The electronic properties can be easily modulated by tuning the length and the nature of the spacer[9-11].

    4΄-Phenyl-2,2΄:6΄,2΄΄-terpyridine (ph-tpy), as an extension of this approach of connecting aromatic rings to the terpyridine moiety ligand, is prominent building block in both organic and inorganic supramolecular chemistry with their π-stacking ability, directional H-bonding and coordination properties. It has attracted widespread attention due to their ability to form complexes with a variety of transition-metal ions, which show remarkable photophysical, photochemical and redox properties based on intra/intermolecular electron and energy transfer[12].

    In this work, we have synthesized and characterized a ligand L, 4΄-phenyl-2,2΄:6΄,2΄΄-terpyridine, and its interactions with selected metal ions (Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ), Ni(Ⅱ), Mn(Ⅱ), Fe(Ⅱ) and Pb(Ⅱ)). To investigate how metal ions interact with ligand L, Fe(L)-based complex 1 was synthesized, and spectroscopic studies and single-crystal X-ray diffraction analysis were performed.

    2. EXPERIMENTAL

    2.1 Physical measurements

    Elemental analyses (C, H, N) were carried out on a Vario MICRO elemental analyzer. Infrared (IR) spectra were recorded on a Nicolet iS 50 FT-IR spectrophotometer using KBr pellets. Electronic absorption spectra were measured on a JASCO V-770 spectrophotometer. 1H NMR and 13C NMR data were collected on an Avance DRX400 (Bruker) in CDCl3 solution containing tetramethylsilane as an internal standard. The solution was contained in a standard 5 mm sample tube. Fluorescence spectra were recorded at room temperature on an F-4600 FL spectrophotometer in a quartz cell (1 cm). Excitation sit was at 2.5 nm, and emission slit was at 5 nm. The scan speed was 1200 nm/min with a PMT voltage at 700 V. All experimental manipulations and data collections were performed at room temperature, unless otherwise stated.

    Stock solution of ligand L (5 × 10–4 mol·L–1) was prepared in acetonitrile and dichloromethane (23:2, V/V). Stock solution of the metal ions (10–2 mol·L–1) was prepared using corresponding salts: Fe(NO3)3·9H2O, Cu(OAc)2⋅H2O, Co(OAc)2⋅4H2O, Cr(NO3)3⋅6H2O, Cd(NO3)2⋅4H2O, (NH4)2Fe(SO4)2·6H2O, Mn(OAc)2⋅4H2O, and ZnCl2⋅6H2O in CH3CN with an exception for Pb(Ⅱ) and Ni(Ⅱ). Instead, PbCl2 and NiCl2 were used and a small amount of water was added to facilitate dissolution in its preparation.

    A typical procedure for the collection of electronic absorption spectroscopic data is as follows: 3.0 mL of a solution of ligand L (1.0 × 10–5 mol·L–1) which was prepared from its stock solution was transferred into a quartz cell (1 cm) and its UV-Vis spectrum (190~900 nm) was recorded. Into the cell was added the stock solution of Cu(Ⅱ) (3.0 μL, 1.0 eq.) and its spectrum was recorded. The above process was repetitively carried out at other concentrations of Cu(Ⅱ). In fluorescent data collection, solutions of ligand L (1.0 × 10–5 mol·L–1) and metal ions (1.0 × 10–2 mol·L–1) were the same as electronic absorption spectroscopy. 3.0 mL of the above solution of ligand L was used in fluorescent measurements. A procedure for examining influence of metal ions on fluorescent spectrum of the ligand was essentially the same as that for measuring electronic absorption spectra.

    2.2 Materials and syntheses

    Unless otherwise noted, all chemicals and starting materials for synthesis were of reagent grade and used without further purification.

    Caution! Perchlorate salts of metal complexes are potentially explosive. So handling them carefully in small quantities is highly suggested for safety considerations.

    2.3 Synthesis of 4΄-phenyl-2,2΄:6΄,2΄΄-terpyridine (L)

    2-Acetylpyridine (2.5 mL, 22.3 mmol) was added to a solution of benzaldehyde (1 mL, 9.8 mmol) in ethanol (50 mL) at room temperature, then a solution of ammonium hydroxide (7 mL, 181.8 mmol) and potassium hydroxide (1.38 g, 24.6 mmol) was added. The mixture was heated and stirred for 12 h at 70 ℃, resulting in white precipitate. The reaction mixture was cooled, and white precipitate was collected by filtration. Recrystallization from dichloromethane-petroleum ether (20mL: 40mL) gave 4΄-phenyl-2,2΄:6΄,2΄΄-terpyridine. Colorless crystals (1.19 g, 39%). 1H NMR (CDCl3, 400MHz): δ (ppm) = 8.70~8.73 (m, 4H), 8.64~8.67 (m, 2H), 7.88~7.91 (m, 2H), 7.82~7.86 (m, 2H), 7.48~7.52 (m, 2H), 7.41~7.45 (m, 1H), 7.30~7.33 (m, 2H); 13C NMR (100MHz, CDCl3), δ (ppm) = 156.26, 155.93, 150.32, 149.15, 138.50, 136.86, 129.03, 128.94, 127.36, 123.83, 121.37, 118.93. IR (KBr pellet, cm-1): 3426s, 3131s, 3087w, 3069w, 3048w, 3010w, 2990w, 1646m, 1600s, 1583vs, 1566s, 1547m, 1466s, 1451w, 1438m, 1391s, 1340vw, 1311vw, 1290w, 1265m, 1223w, 1191w, 1168w, 1130m, 1098w, 1075m, 1041m, 996w, 986w, 965w, 916w, 906w, 895s, 847w, 821w, 796s, 759s, 734s, 692w, 681s, 659s, 617s. UV-vis (CH3CN): λmax, nm (ε, dm3 mol–1 cm–1): 200 (74483), 226 (23273), 252 (39162), 275 (36761), 321 (7386).

    2.4 Synthesis of Fe(L)2(ClO4)2⋅2CH3CN (1)

    To a solution of ammonium ferrous sulfate (200 mg, 0.5 mmol) in water (5 mL), a solution of L (324 mg, 1.0 mmol) in dichloromethane (25 mL) was added at room temperature. The mixture was stirred at 30 ℃ for three hours, which resulted in a purple solution. Then sodium perchlorate hydrate (149 mg, 1.1 mmol) was added to the above reaction solution. A purple dark purple precipitate appeared immediately and was collected by filtration. Deep purple crystals (186.3 mg, 39%) of 1 suitable for X-ray diffraction were obtained by slow diffusion of diethylether (30 mL) into the CH3CN (10 mL) solution of the purple precipitate at room temperature. Elemental analysis for C46H36Cl2FeN8O8, Anal. Calcd.: C, 57.82; H, 3.80; N, 11.73%. Found: C, 57.24; H, 3.65; N, 11.57%. IR (KBr pellet, cm-1): 3238w, 3106vw, 3067vw, 3001vw, 1638s, 1615s, 1576vw, 1558w, 1540w, 1506w, 1485m, 1469m, 1458vw, 1449vw, 1436vw, 1419s, 1361w, 1338w, 1286w, 1247w, 1145vw, 1101m, 1088m, 1035w, 1000w, 940w, 890vw, 873w, 793s, 764s, 433w, 684w, 653w, 637w, 624s, 508w. UV-vis (CH3CN): λmax, nm (ε, dm3·mol–1·cm–1): 201 (108159), 243 (32553), 275 (60932), 285 (48283), 320 (57413), 364 (7736), 565 (24908).

    2.5 X-ray crystal structure determination

    The single crystal data of complex 1 were collected on a Saturn724+ diffractometer equipped with graphite-monochromatic MoKα (λ = 0.71073 Å) radiation using an ω scan mode at 123 K. The structure was solved by direct methods with SHELXL-2016 program[13] and refined by full-matrix leastsquares (SHELXL-2016) on F2. Hydrogen atoms were calculated geometrically and refined using a riding model. Anisotropic thermal parameters were used for the non-hydrogen atoms, and isotropic parameters were used for the hydrogen atoms. All non-hydrogen atoms were refined by full-matrix least-squares on F2. The R values are defined as wR = Σ||Fo| – |Fc||/Σ|Fo| and wR = [Σ[w(Fo2 – Fc2)2]/Σ[w(Fo2)2]]1/2. Selected bond lengths and bond angles for complex 1 are presented in Table 1.

    Table 1

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) for Complex 1
    DownLoad: CSV
    Bond Dist. Bond Dist. Bond Dist.
    Fe(1)–N(1) 1.9956(17) Fe(1)–N(3) 2.0090(17) Fe(1)–N(5) 1.9266(16)
    Fe(1)–N(2) 1.8775(16) Fe(1)–N(4) 2.1218(17) Fe(1)–N(6) 2.1530(17)
    Angle (°) Angle (°) Angle (°)
    N(1)–Fe(1)–N(2) 80.50(7) N(2)–Fe(1)–N(3) 181.19(7) N(3)–Fe(1)–N(5) 97.71(7)
    N(1)–Fe(1)–N(3) 161.42(7) N(2)–Fe(1)–N(4) 102.54(7) N(3)–Fe(1)–N(6) 94.40(6)
    N(1)–Fe(1)–N(4) 89.24(7) N(2)–Fe(1)–N(5) 177.97(7) N(4)–Fe(1)–N(5) 79.16(7)
    N(1)–Fe(1)–N(5) 100.68(7) N(2)–Fe(1)–N(6) 99.90(7) N(4)–Fe(1)–N(6) 157.39(6)
    N(1)–Fe(1)–N(6) 91.81(6) N(3)–Fe(1)–N(4) 91.69(7) N(5)–Fe(1)–N(6) 78.46(6)

    3. RESULTS AND DISCUSSION

    3.1 Synthesis and characterization

    The desired ligand L, 4΄-phenyl-2,2΄:6΄,2΄΄-terpyridine, was prepared by a Krohnke-type synthesis (Scheme 1)[14, 15]. Treatment of one equivalent of benzaldehyde with two equivalents of 2-acetylpyridine and ammonium hydroxide in potassium hydroxide solution afforded the target ligand L as a white solid, which was characterized by IR, elemental analysis, electronic absorption spectra, 1H NMR and 13C NMR.

    Scheme 1

    Scheme 1.  Synthetic route of ligand L
    DownLoad: Full-Size Img PowerPoint

    Complex 1 was obtained by reaction of (NH4)2Fe(SO4)2 with ligand L in the presence of NaClO4, which was characterized by IR, electronic absorption spectra, elemental analysis and singlecrystal X-ray diffraction analysis.

    3.2 Electronic absorption spectroscopy

    The electronic absorption spectrum of ligand L shows strong absorption bands at 200 nm (ε = 74483 L·mol–1·cm–1), 226 nm (ε = 23273 L·mol–1·cm–1), 252 nm (ε = 39162 L·mol–1·cm–1), 275 nm (ε = 36761 L·mol–1·cm–1) and 321 nm (ε = 7386 L·mol–1·cm–1) in acetonitrile-dichloromethane (24:1, V/V), as shown in Fig. 1, which can be assigned to π→π* transitions. These absorption bands are of characteristic features of compounds possessing pyridine moiety[16].

    Figure 1

    Figure 1.  Effect of selected metal ions (10 eq.) on the electronic absorption spectrum of the ligand L (1.0 × 10–5 mol·L–1)
    DownLoad: Full-Size Img PowerPoint

    The interactions of ligand L with selected metal ions, such as Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ), were investigated employing electronic absorption spectroscopy, as shown in Fig. 1-5 and S1-S16 in Supporting Information. As the results are similar, here only the interaction of Cu(Ⅱ) ion with ligand L is shown. Upon addition of Cu(Ⅱ) ion into the Ligand, the intensity of bands λmax of 200, 275 and 321 nm increase, and these peaks have little red-shift, companied with the band at λmax of 252 nm that has disappeared (Fig. 2 and 3). For the interaction of Fe(Ⅱ) ion with ligand L, a new band at 565 nm appears (Fig. 4), and it is neither from the precursors (NH4)2Fe(SO4)2 nor ligand L (Fig. 5). The similar phenomenon occurs in the interaction of Pb(Ⅱ) ion with ligand L (Fig. S15 and S16).

    Figure 2

    Figure 2.  Electronic absorption spectrum of ligand L, Cu(Ⅱ) ion and L + Cu(Ⅱ) ion (10 eq.) on the electronic absorption spectrum of the ligand L (1.0 × 10–5 mol·L–1)
    DownLoad: Full-Size Img PowerPoint

    Figure 3

    Figure 3.  Spectral variation of the ligand in acetonitrile-dichloromethane (V:V = 24:1) (1.0 × 10–5 mol·L–1) upon addition of Cu(Ⅱ)
    DownLoad: Full-Size Img PowerPoint

    Figure 4

    Figure 4.  Spectral variation of the ligand in acetonitrile-dichloromethane (V:V = 24:1) (1.0 × 10–5 mol·L–1) upon addition of Fe(Ⅱ)
    DownLoad: Full-Size Img PowerPoint

    Figure 5

    Figure 5.  Electronic absorption spectrum of ligand L, Fe(Ⅱ) ion and L + Fe(Ⅱ) ion (10 eq.) on the electronic absorption spectrum of the ligand L (1.0 × 10–5 mol·L–1)
    DownLoad: Full-Size Img PowerPoint

    In order to explore how Fe(Ⅱ) ion interacts with ligand L and hence influences its electronic spectra, complex 1 was synthesized and their electronic absorption spectroscopy was investigated. The electronic absorption spectroscopy of complex 1 is similar to that of the interaction of Fe(Ⅱ) with Ligand L (Fig. 6). The appearance of the bands for complex 1 at λmax of 565 nm can be assigned to metal-to-ligand charge transfer[17, 18] (MLCT). Also the new band at 565 nm for the interaction of Fe(Ⅱ) or Pb(Ⅱ) with ligand L should be assigned to MLCT.

    Figure 6

    Figure 6.  Electronic absorption spectrum of ligand L and complex 1 in an acetonitrile-dichloromethane (V:V = 24:1) solution (1.0 × 10–5 mol·L–1)
    DownLoad: Full-Size Img PowerPoint

    3.3 Fluorescence emission spectroscopy

    To investigate the selectivity of ligands to metal ions, the fluorescence emission spectroscopy of ligand L and selected metal ions was meaured upon excitation at 280 nm. The fluorescence emission spectroscopy of ligand L exhibits a strong fluorescent emission peak at 354 nm in acetonitrile-dichloromethane (V:V = 24:1) solution at room temperature with the concentration of 1.0 × 10–5 mol·L–1.

    For Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Co(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ) ions, addition of the metal ion weakened steadily the fluorescence intensity of the ligand and resulted in completely quenching upon excitation at 280 nm (Figs. 7 and 8 and S17-22). The weakening of fluorescence can be assigned to the energy transfer from the ligand to the metal ion after the ligand is coordinated to the metal ion, resulting in fluorescence quenching.

    Figure 7

    Figure 7.  Fluorescence emission spectra of ligand L (1.0 × 10–5 mol·L–1) in an acetonitrile-dichloromethane (V:V = 24:1) solution upon the addition of Cu(Ⅱ) ion (λex = 280 nm)
    DownLoad: Full-Size Img PowerPoint

    Figure 8

    Figure 8.  Fluorescence emission spectra of ligand L (1.0 × 10–5 mol·L–1) in an acetonitrile-dichloromethane (V:V = 24:1) solution upon the addition of Fe(Ⅲ) ion (λex = 280 nm)
    DownLoad: Full-Size Img PowerPoint

    For Zn(Ⅱ) and Cd(Ⅱ) ions, the fluorescence intensity of the ligand increases upon addition of the metal ion with excitation at 280 nm (Fig. 9 and S23). The strong fluorescence enhancement may be attributed to the fact that Zn(Ⅱ) and Cd(Ⅱ) are located in the same family of the periodic table of elements and have similar d10 electronic structure characteristics. Moreover, when the electron pair of N atom is bound by coordination of Zn(Ⅱ) or Cd(Ⅱ), the electron transfer process from the tpy to the fluorophore is blocked and the fluorescence is switched on, leading to a significant emission fluorescence enhancement.

    Figure 9

    Figure 9.  Fluorescence emission spectra of ligand L (1.0 × 10–5 mol·L–1) in an acetonitrile-dichloromethane (V:V = 24:1) solution upon the addition of Zn(Ⅱ) ion (λex = 280 nm)
    DownLoad: Full-Size Img PowerPoint

    The fluorescence emission spectroscopy of complex 1 was also meaured upon excitation at 280 nm. Complex 1 exhibits a strong band at 310 nm in acetonitrile-dichloromethane (V:V = 24:1) solution at room temperature with concentration of 1.0 × 10–5 mol·dm–3 (Fig. 10), which could be assigned to the Fe(dπ) → L (π*) MLCT[8]. Compared to ligand L, the band intensity of complex 1 at 310 nm increased, and the band at 354 nm vanished.

    Figure 10

    Figure 10.  Fluorescence emission spectra of ligand L and complex 1 in an acetonitrile-dichloromethane (V:V = 24:1), solution (1.0 × 10–5 mol·L–1)
    DownLoad: Full-Size Img PowerPoint

    3.4 Molecular structure

    A perspective view of the cationic complex 1 is shown in Fig. 11. Selected bonding parameters are given in Table 1. Complex 1 crystallizes in the monoclinic space group P21/n, containing one [Fe(L)]2+ unit with two positive charges balanced by two ClO4- anions and two more uncoordinated acetonitrile solvent molecules. The Fe center in 1 defines a distorted octahedral coordinated environment, and is linked by six nitrogen atoms from two ligands L. The Fe–N(2) and Fe–N(5) axial bonds involving the pyridine rings are markedly shorter than the equatorial bonds (Fe–N(1), Fe–N(3), Fe–N(4) and Fe–N(6)) as observed for [Fe(L)2]-(PF6)2[19], [Fe(L)2](FeCl4)[20] and [Fe(L)2](NO3)2[21]. The dihedral angle between two tpy moieties is 89.8o, suggesting essentially perpendicular orientation of the ligands with respect to each other. The torsion angles between the tpy moiety and the phenyl group are 20.1o and 28.4o, and this compares to 32o and 41o in [Fe(L)2](PF6)2(DMF)2[22]. The shortest intermolecular distance of Fe⋅⋅⋅Fe is 8.656 Å for 1. The crystal structures of [Cu(L)2]2+[23, 24], [Zn(L)2]2+[25], [Cd(L)2]2+[26], [Ni(L)2]2+[27, 28], [Co(L)2]2+[29-31], [Mn(L)2]2+[32, 33], Cr(L)2]3+[34, 35] and [Pb(L)2]2+[36] have been reported in the literature, similar to the structure of complex 1.

    Figure 11

    Figure 11.  ORTEP view of the heteronuclear complex 1 with an atom-numbering scheme at the 30% probability level. Hydrogen atoms, solvent molecules and anions have been omitted for clarity
    DownLoad: Full-Size Img PowerPoint

    4. CONCLUSION

    In conclusion, ligand L was synthesized and well characterized by IR, electronic absorption spectra, elemental analysis, 1H NMR and 13C NMR. Interactions of the ligand with selected metal ions, such as Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ), were investigated by electronic absorption spectroscopy and fluorescent properties. The study indicates ligand L has an excellent selectivity for Zn(Ⅱ) and Cd(Ⅱ) ions by fluorescent enhancement.


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  • Scheme 1  Synthetic route of ligand L

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    Figure 1  Effect of selected metal ions (10 eq.) on the electronic absorption spectrum of the ligand L (1.0 × 10–5 mol·L–1)

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    Figure 2  Electronic absorption spectrum of ligand L, Cu(Ⅱ) ion and L + Cu(Ⅱ) ion (10 eq.) on the electronic absorption spectrum of the ligand L (1.0 × 10–5 mol·L–1)

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    Figure 3  Spectral variation of the ligand in acetonitrile-dichloromethane (V:V = 24:1) (1.0 × 10–5 mol·L–1) upon addition of Cu(Ⅱ)

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    Figure 4  Spectral variation of the ligand in acetonitrile-dichloromethane (V:V = 24:1) (1.0 × 10–5 mol·L–1) upon addition of Fe(Ⅱ)

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    Figure 5  Electronic absorption spectrum of ligand L, Fe(Ⅱ) ion and L + Fe(Ⅱ) ion (10 eq.) on the electronic absorption spectrum of the ligand L (1.0 × 10–5 mol·L–1)

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    Figure 6  Electronic absorption spectrum of ligand L and complex 1 in an acetonitrile-dichloromethane (V:V = 24:1) solution (1.0 × 10–5 mol·L–1)

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    Figure 7  Fluorescence emission spectra of ligand L (1.0 × 10–5 mol·L–1) in an acetonitrile-dichloromethane (V:V = 24:1) solution upon the addition of Cu(Ⅱ) ion (λex = 280 nm)

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    Figure 8  Fluorescence emission spectra of ligand L (1.0 × 10–5 mol·L–1) in an acetonitrile-dichloromethane (V:V = 24:1) solution upon the addition of Fe(Ⅲ) ion (λex = 280 nm)

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    Figure 9  Fluorescence emission spectra of ligand L (1.0 × 10–5 mol·L–1) in an acetonitrile-dichloromethane (V:V = 24:1) solution upon the addition of Zn(Ⅱ) ion (λex = 280 nm)

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    Figure 10  Fluorescence emission spectra of ligand L and complex 1 in an acetonitrile-dichloromethane (V:V = 24:1), solution (1.0 × 10–5 mol·L–1)

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    Figure 11  ORTEP view of the heteronuclear complex 1 with an atom-numbering scheme at the 30% probability level. Hydrogen atoms, solvent molecules and anions have been omitted for clarity

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    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) for Complex 1

    Bond Dist. Bond Dist. Bond Dist.
    Fe(1)–N(1) 1.9956(17) Fe(1)–N(3) 2.0090(17) Fe(1)–N(5) 1.9266(16)
    Fe(1)–N(2) 1.8775(16) Fe(1)–N(4) 2.1218(17) Fe(1)–N(6) 2.1530(17)
    Angle (°) Angle (°) Angle (°)
    N(1)–Fe(1)–N(2) 80.50(7) N(2)–Fe(1)–N(3) 181.19(7) N(3)–Fe(1)–N(5) 97.71(7)
    N(1)–Fe(1)–N(3) 161.42(7) N(2)–Fe(1)–N(4) 102.54(7) N(3)–Fe(1)–N(6) 94.40(6)
    N(1)–Fe(1)–N(4) 89.24(7) N(2)–Fe(1)–N(5) 177.97(7) N(4)–Fe(1)–N(5) 79.16(7)
    N(1)–Fe(1)–N(5) 100.68(7) N(2)–Fe(1)–N(6) 99.90(7) N(4)–Fe(1)–N(6) 157.39(6)
    N(1)–Fe(1)–N(6) 91.81(6) N(3)–Fe(1)–N(4) 91.69(7) N(5)–Fe(1)–N(6) 78.46(6)
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  • 发布日期:  2020-04-01
  • 收稿日期:  2018-12-25
  • 接受日期:  2019-04-09
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