Two Polynuclear Fe Complexes with Boat-like Core: Syntheses, Structures and Magnetic Properties

Na YANG Hua YANG Hai-Quan TIAN Da-Cheng LI Jian-Min DOU

Citation:  Na YANG, Hua YANG, Hai-Quan TIAN, Da-Cheng LI, Jian-Min DOU. Two Polynuclear Fe Complexes with Boat-like Core: Syntheses, Structures and Magnetic Properties[J]. Chinese Journal of Structural Chemistry, 2022, 41(3): 2203047-2203054. doi: 10.14102/j.cnki.0254-5861.2011-3311 shu

Two Polynuclear Fe Complexes with Boat-like Core: Syntheses, Structures and Magnetic Properties

English

  • Coordination complexes have attracted considerable attention due to their charming structures and various properties in the areas of molecular magnetism, catalysis, luminescence, bioactivities and so on[1-5]. Moreover, metal complexes not only exhibit definitive structures and metal coordination environment, but also serve as remarkable candidates to study single molecule magnets (SMMs). The magnetic performance reveals that the magnetic properties depend on the paramagnetic metal ions, such as transition metal ions (MnIII, FeIII, CoII)[6-8] and lanthanide ions (DyIII, TbIII, ErIII)[9, 10], the coupling interactions, as well as the effect of ligand field[11-14]. While solvent molecules, assistant ligands and/or other anions can influence the supramolecular structures and coordination enviroment, which would further change the ligand-field of metal centers. As a result, magnetic behavior would be influenced or changed[15]. Usually, in the design of complexes, the researcher will combine the paramagnetic metal ions with the large magnetic anisotropy or high spin-orbit coupling and multidendate ligand into an experiment process, and/or add the second assistant ligand to enrich the structures and properties. Therefore, it is promising to obtain the expected products through choosing suitable ligands and metal ions, as well as controlling the coordination environment through assistant ligand or solvent molecules, and further explore the supramolecular interactions and relevant properties.

    Metallacrowns (MCs) are inorganic metal macrocyclic complexes, regarded as metal ions and nitrogen atoms replacing the methylene carbon atoms of crown ethers to exhibit -[M–N–O]-repeat unit in their ring[16, 17]. Since Pecoraro and Lah reported the first metallacrown in 1989, a variety of metallacrowns have been synthesized with the structural types consisting of 9-MC-3, 12-MC-4, 15-MC-5, 18-MC-6, 24-MC-8, 30-MC-10, 45-MC-12 and 60-MC-20. The reaserch fields involved coordination polymers[18-20], molecular magnetisms[21, 22], luminescence[23, 24] and magnetic resonance imaging contrasts[25]. Numerous homometallic FeIII MCs have been reported with the structure Containing FeIII[9-MCFeN(shi)III-3][26], CuII[12-MCFeN(Shi)III-4][27], [18-MCFeIII-6][28, 29], and their magnetocaloric effect has been discussed in detail. The recent studies of molecular magnets showed that the high spin FeIII complexes with S = 5/2 spin state presented spin crossover (SCO)[30, 31]. Herein, in our experiment process, we chose tetradentate Schiff-base ligands (N-(2-hydroxyethyl)-3-methoxysalicylaldimin H2L) with rich N, O donors, high-spin FeIII ions as well as the bridging sodium nitroprusside to synthesize Fe-based complexes. Successfully, two polynuclear complexes {NaFe4(μ4-O)(L)4(μ2-Cl)[Fe(CN)5NO](H2O)(DMF)2} and {NaFe4(μ4-O)(L)4(μ2-OEt)[Fe(CN)5NO](H2O)(DMF)2} were obtained, and their structures were characterized through X-ray singlecrystal diffraction, elemental analysis, IR and spectroscopic analysis, as well as their supramolecular frameworks and magnetic properties were explored in detail.

    All the chemical materials were commercially available and used as received. Elemental analyses for C, H, and N were acquired using an Elementar Vario EL analyzer. The infrared spectra were recorded from KBr disks in the range of 400~4000 cm-1 on a Nicolet iS50 FT-IR spectrometer. Powder X-ray diffraction patterns were obtained on a Smart Lab. Variable temperature magnetic susceptibility measurements were carried out on a Quantum Design MPMS-XL7 SQUID magnetometer.

    A solution of o-vanillin (0.1522 g, 1 mmol) and ethanolamine (0.0611 g, 1 mmol) in 12 mL N, N-dimethylformamide (DMF) was stirred for 0.5 h at room temperature. With stirring, triethylamine (0.1012 g, 1 mmol) was added into the above solution, and then FeCl3·6H2O (0.2703 g, 1 mmol) was added to the above solution. After stirring for 2 h, the mixture became black. Then, a solid Na2[Fe(CN)5NO]·2H2O (0.2979 g, 1 mmol) was added and the mixture was stirred for another 2 h. The solution was filtered and the filtrate was layered with EtOH and Et2O. The black block crystals suitable for X-ray analysis were obtained within a week with about 48% yield on Fe. Anal. Calcd. (%) for C51H59ClFe5N12NaO17: C, 42.28; H, 4.04; N, 11.60. Found: C, 42.25; H, 4.08; N, 11.57. IR (KBr, cm−1): 3431 (br), 2933 (br), 2142 (w), 1885 (s), 1633 (vs), 1552 (w), 1471 (m), 1391 (w), 1305 (m), 1222 (s), 1035 (w), 971 (w), 865 (w), 739 (m), 632 (w), 524 (w).

    A solution of o-vanillin (0.1522 g, 1 mmol) and ethanolamine (0.0611 g, 1 mmol) in 9 mL DMF and 3 mL acetonitrile was stirred for 0.5 h at room temperature. With stirring, triethylamine (0.2024 g, 2 mmol) was added into the above solution. Then, into the light yellow solution, FeCl3·6H2O (0.2703 g, 1 mmol) was added. After stirring for 2 h, the mixture became black, and a solid, Na2[Fe(CN)5NO]·2H2O (0.2979 g, 1 mmol), was added followed by further stirring for another 2 h. The solution was filtered and the filtrate was layered with EtOH and Et2O. The black block crystals suitable for X-ray analysis were obtained within a week with about 45% yield based on Fe. Anal. Calcd. (%) for C53H65Fe5N12NaO18: C, 43.55; H, 4.45; N, 11.50. Found (%): C, 43.58; H, 4.43; N, 11.48. IR (KBr, cm−1): 3423 (br), 2922 (br), 2141 (w), 1885 (s), 1633 (vs), 1552 (w), 1471 (m), 1391 (w), 1307 (m), 1221 (s), 1035 (w), 972 (w), 865 (w), 739 (m), 619 (w), 426 (w).

    X-ray diffraction data for 1 and 2 were obtained on anAgilent Xcalibur Eos Gemini CCD plate diffractometer equipped with graphite monochromatic Cu radiation (λ = 1.54184 Å). All the crystal structures were solved by direct methods using the SHELXS-18 program and refined by the full-matrix least-squares on F2 using the SHELXL program[32]. Non-hydrogen atoms are refined with displacement temperature parameters. Hydrogen atoms of the organic ligand are theoretically determined with isotropic thermal displacement parameters. Table 1 shows the crystal data and structure refinement of 1 and 2. Selected bond lengths and bond angles for 1 and 2 are listed in Table S3 and Table S4.

    Table 1

    Table 1.  Crystal Data and Structure Refinement for 1 and 2
    DownLoad: CSV
    Crystal data 1 2
    Empirical formula C51H59ClFe5N12NaO17 C53H65Fe5N12NaO18
    Formula weight 1449.79 1460.41
    Crystal system Triclinic Triclinic
    Space group P$ \overline 1 $ P$ \overline 1 $
    a (Å) 15.6357(1) 13.9367(1)
    b (Å) 16.5733(2) 14.5856(2)
    c (Å) 17.6867(1) 20.3766(4)
    α (º) 71.111(6) 80.084(7)
    β (º) 84.047(5) 74.149(7)
    γ (º) 71.735(6) 68.295(8)
    Volume (Å3) 4117.9(5) 3690.3(5)
    Z 2 2
    Dc (g/cm3) 1.169 1.314
    μ (Cu) (mm-1) 7.734 8.319
    λ (Å) 1.54184 1.54184
    F(000) 1486 1504
    Crystal size (mm) 0.120 × 0.110 × 0.100 0.130 × 0.120 × 0.110
    T (K) 293(2) 134(2)
    S 0.869 0.924
    Reflections collected 29458 27798
    R and wR (I > 2σ(I)) 0.0643, 0.1527 0.0703, 0.1532
    R and wR (all data) 0.1144, 0.2624 0.1334, 0.2743

    The reaction of FeCl3·6H2O with N-(2-hydroxyethyl)-3-methoxysalicylaldimine (H2L) in a 1:1 molar ratio in DMF solution yielded complexes {NaFe4(μ4-O)(L)4(μ2-Cl)[Fe-(CN)5NO](H2O)(DMF)2} (1) and {NaFe4(μ4-O)(L)4(μ2-OEt)-[Fe(CN)5NO](H2O)(DMF)2} (2). It can be seen from Scheme 1 that 1 was isolated with a chloride bridging two Fe ions, while the addition of MeCN solvent resulted into the information of 2 with one μ2-OEt replacing μ2-Cl- to bridge two Fe ions. The PXRD of the crystals revealed the purity of 1 and 2 in Fig. S1.

    Scheme 1

    Scheme 1.  Syntheses of 1 and 2

    Complex 1 crystallizes in P$ \overline 1 $ space group and triclinic crystal system (Table 1) with the molecular structure exhibi-ting a trigonal bipyramidal configuration, where three Fe ions are located in the triangle core and one Fe and one Na occupy the apical positions. The simple presentation of the molecular structure is shown in Fig. 1(a). Three Fe ions from the equatorial plane are held together through one μ4-O atom with the other coordination atoms supplied by four ligands, and one H2O molecule, one bridge μ2-Cl ion as well as one N atom from [Fe(CN)5NO]2-. Four ligands exhibit two coordination modes, η1: η2: η1: η2: μ3 and η1: η1: η2: μ2 (Scheme 2). Three Fe ions are located in a hexa-coordination enviro-nment. For Fe(4), the coordination atoms consist of three donors (O(2), N(4), O(3)) of one ligand, one bridge μ2-Cl(1) and one μ4-O(18), as well as one O(9) atom from the second ligand; the coordinate atoms of Fe(5) come from three donors (O(12), N(1), O(13)) of one ligand, one bridge μ2-Cl(1) and one μ4-O(18), as well as one O(7) atom from a water molecule; while for Fe(1), the coordination atoms are supplied by three donors (O(8), N(3), O(9)) of one ligand, one μ4-O(18) and one N(9) atom from [Fe(CN)5NO]2-, one μ2-O(6) which further bridges Fe(1) and Fe(3). Fe(3) and Na(1) occupying the apical positions are also hexacoordinated. For Fe(3), the coordination atoms come from three donors (O(5), N(2), O(6)) of one ligand and one O(15) atom from a DMF molecule, as well as two μ2-O (O(3), O(13)) atoms of two ligands; for Na(1), the coordination atoms consist of one μ4-O(18) and one O(14) atom of a DMF molecule, as well as four coordinated O (O(1), O(2), O(11), O(12)) atoms of two ligands. The metal skeleton of 1 is also described as a "boat-like" core constructed through three Fe ions and one Na ion with the fourth Fe ion acting as "paddle" or " ship man" (Fig. 2(a)). The "hull bottom" contains a metallamacrocycle with metallacrown-like motif (Fig. 2(b)). The analogue of metallacrown can be recognized as an 8-MC-4 type with adjacent metal connected by O atom to exhibit [-M-O-] repeat unit. There are two different bridging groups among the metal centrals. The Fe–O–Fe angles are 125.3(2)° for Fe(3)–O(3)–Fe(4) and 123.7(2)° for Fe(3)–O(13)–Fe(5). The Fe–O–Na(1) angles are 103.56(9)° and 104.1(2)° for Fe(4)–O(2)–Na(1) and Fe(5)–O(12)–Na(1), respectively. The coordination configurations of Fe and Na were calculated by SHAPE[33]. All Fe ions are all distorted octahedral configurations. The coordinated geometry of Na ion is close to C5v configuration. The specific coordination configuration data of Fe and Na ions are listed in Table 2. The oxidation states of Fe are determined according to the molecule structure, charge balance and BVS calculations[34]. The BVS calculation data are shown in Table 3.

    Figure 1

    Figure 1.  Molecular structures of (a) 1 and (b) 2

    Scheme 2

    Scheme 2.  Coordination modes of L

    Figure 2

    Figure 2.  (a) A boat-like core with a hypothetical personrowing, (b) Analogous [8-MC-4] metallacrown-like motif

    Table 2

    Table 2.  Na and Fe Ion Coordination Configurations for 1 and 2
    DownLoad: CSV
    Hexagon
    (D6h)
    Pentagonal
    pyramid (C5v)
    Octahedron
    (Oh)
    Trigonal prism
    (D3h)
    Johnson pentagonal pyramid J2 (C5v)
    1 Na(1) 23.40 5.08 20.16 7.43 8.17
    Fe(1) 29.98 22.16 1.24 10.81 25.72
    Fe(2) 33.01 28.36 0.27 15.92 31.56
    Fe(3) 32.36 27.79 0.34 15.07 30.99
    Fe(4) 33.62 24.46 1.88 11.75 27.89
    Fe(5) 32.31 26.30 1.37 14.92 29.24
    2 Na(1) 22.49 6.98 18.90 5.81 10.61
    Fe(1) 33.54 22.05 1.75 10.98 26.13
    Fe(2) 30.58 23.12 1.23 12.15 26.50
    Fe(3) 30.38 22.21 1.25 10.70 25.87
    Fe(4) 32.63 28.65 0.22 15.84 31.72
    Fe(5) 32.43 27.16 0.34 14.82 30.63

    Table 3

    Table 3.  Bond Valence Calculations (BVS) for 1 and 2
    DownLoad: CSV
    Atoms +2 +3
    1 Fe(1) 2.64 3.10
    Fe(3) 2.64 3.13
    Fe(4) 2.57 3.01
    Fe(5) 2.62 3.06
    2 Fe(1) 2.71 3.18
    Fe(2) 2.70 3.16
    Fe(3) 2.62 3.08
    Fe(5) 2.62 3.11

    With deep analysis of the interactions among molecules, we found a larger number of hydrogen bonds and π-π stacking interactions. As shown in Fig. 3(a), there are two types of hydrogen bonds between molecules, (C(8)–H(8)∙∙∙N(11), C(31)–H(31C)∙∙∙N(11), C(19)–H(19A)∙∙∙N(7), C(34)–H(34)∙∙∙N(7), C(41)–H(41C)∙∙∙N(10)) and C–H∙∙∙Cl (C(4)–H(4)∙∙∙Cl(1)), and two types of π-π stacking interactions (Cg5∙∙∙Cg5 and Cg4∙∙∙Cg8). The distances between two centers for Cg4∙∙∙Cg8 (Fig. 3(b)) and Cg5∙∙∙Cg5 (Fig. 3(c)) are 3.9628(3) and 3.6691(3) Å, respectively. The angles between the two centers for Cg4∙∙∙Cg8 and Cg5∙∙∙Cg5 are 5° and 0°, respectively. These rich intermolecular interactions lead to the formation of a three-dimensional supramolecular structure (Fig. 3(d)). The specific parameters of hydrogen bonds and π-π stacking interactions can be obtained from Table S1 and Table S2.

    Figure 3

    Figure 3.  (a) Intermolecular interactions of 1, π-π stacking interactions of (b) Cg4∙∙∙Cg8 and (c) Cg5∙∙∙Cg5, (d) 3D supramolecular structure of 1

    Complex 2 crystallizes in P$ \overline 1 $ space group of triclinic crystal system (Table 1), and the difference with the structure of complex 1 is that the deprotonated μ2-OEt anion displaces μ2-Cl- anion to bridge Fe(1) and Fe(2). The molecular structure of 2 is shown in Fig. 1(b). The coordinated geometry of Na ion is close to D3h configuration. The specific coordination configuration data and BVS calculation data of Fe and Na ions are listed in Tables 2 and 3, respectively. In 2, the three-dimensional supramolecular structure (Fig. 4(b)) is further constructed through C(30)–H(30A)∙∙∙N(23), C(1D)–H(1D2)∙∙∙N(24) and C(1G)–H(1G2)∙∙∙N(24) interactions (Fig. 4(a)). Detailed data for these hydrogen bonds are also given in Table S1.

    Figure 4

    Figure 4.  (a) Hydrogen bonds and (b) 3D supramolecular structure of 2

    For 1 and 2, variable temperature magnetic susceptibilities (χMT) have been measured in the range of 1.8~300 K at 1000 Oe dc. The χMT values of 1 and 2 at 300 K are 5.41 and 7.00 cm3∙K∙mol-1, respectively, lower than the expected value of 17.51 cm3∙K∙mol-1 for four independent non-interacting FeIII (S = 5/2, g = 2) (Fig. 5(a) and 5(c)). As [Fe(CN)5NO]2- is diamagnetic, the exchange interaction between FeII and FeIII through the cyanide bridging ligand is negligible[35]. With decreasing the temperature, magnetic susceptibility values gradually decrease and reach 0.09 and 0.05 cm3∙K∙mol-1 for 1 and 2 at 1.8 K, respectively. This phenomenon reveals that the interaction between four FeIII ions is antiferromagnetic coupling. The experimental susceptibility data were fitted through PHI software[36] with the best-fitting parameters of J1 = –11.3, J2 = –16.4, J3 = –19.2 cm–1 for 1 and J1 = –21.8, J2 = –11.5 cm–1 for 2, respectively. The field depended magnetization (M) curves of 1 and 2 at different temperature are shown in Fig. 5(b) and 5(d), respectively. M values increase linearly at low field without reaching the saturation at highfield region. The curves of M vs H/T at different temperature also does not overlap, suggesting the presence of magnetic anisotropy. In order to further study the magnetic properties of 1 and 2, we measured the ac magnetic susceptibility at 0 and 2000 Oe dc fields, respectively, with the frequency range of 1~999 Hz and temperature range from 2 to 12 K. The analysis of ac magnetic susceptibilities finds that the in-phase (χ'M) and out-of-phase (χ"M) of 1 and 2 do not show obvious frequency dependence at two fields. Here, only 2000 Oe field-induced χ'M and χ"M plots are given in Fig. 6. A reason likely derives from the structural symmetry, which offsets the magnetic coupling interaction and makes the title complexes exhibit unsatisfactory magnetic behavior[37].

    Figure 5

    Figure 5.  Plots of χMT vs. T (a) and M/B vs. H/T (b) for 1; Plots of χMT vs. T (c) and M/B vs. H/T (d) for 2

    Figure 6

    Figure 6.  The ac susceptibility temperature dependent diagram at 2000 Oe field: plots of χ'M vs. T (a) and χ"M vs. T(b) of 1; plots of χ'M vs. T (c) and χ"M vs. T (d) of 2

    We obtained two novel polynuclear Fe complexes, where four Fe ions and one Na ion exhibited a trigonal bipyramidal arrangement with three Fe ions locating in the triangle core, and one Fe and one Na ions occupying the apical positions. The metal skeleton is also described as a "boat-like" core constructed through three Fe and one Na ions with the fourth Fe ion acting as the "paddle" or "ship man". The "hull bottom" contains a metallamacrocycle with metallacrown-like motif. The analogue of metallacrown can be recognized as an 8-MC-4 type with adjacent metal connected by O atom to exhibit [-M-O-] repeat unit. In 1, a three-dimensional structure is constructed by hydrogen bonds and π-π stacking interactions. 2 also represents a three-dimensional structure, in which the involved supramolecular interactions consist of hydrogen bonds. Magnetic studies have revealed the presence of antiferromagnetic coupling between metal centers, and the structural symmetry likely offset the magnetic coupling interaction.


    1. [1]

      Nkabyo, H. A.; Barnard, I.; Koch, K. R.; Luckay, R. C. Recent advances in the coordination and supramolecular chemistry of monopodal and bipodal acylthiourea-based ligands. Coord. Chem. Rev. 2021, 427, 213588‒213611. doi: 10.1016/j.ccr.2020.213588

    2. [2]

      Bernot, K.; Daiguebonne, C.; Calvez, G.; Yan, S.; Guillou, O. A journey in lanthanide coordination chemistry: from evaporable dimers to magnetic materials and luminescent devices. Acc. Chem. Res. 2021, 54, 427‒440. doi: 10.1021/acs.accounts.0c00684

    3. [3]

      Saha, K.; Roy, D. K.; Dewhurst, R. D.; Ghosh, S.; Braunschweig, H. Recent advances in the synthesis and reactivity of transition metal σ-borane/borate complexes. Acc. Chem. Res. 2021, 54, 1260‒1273. doi: 10.1021/acs.accounts.0c00819

    4. [4]

      Tsave, O.; Halevas, E.; Yavropoulou, M. P.; Papadimitriou, A. K.; Yovos, J. G.; Hatzidimitriou, A. Structure-specific adipogenic capacity of novel, well-defined ternary Zn(II)-Schiff base materials. Biomolecular correlations in zinc-induced differentiation of 3T3-L1 pre-adipocytes to adipocytes. J. Inorg. Biochem. 2015, 152, 123‒137. doi: 10.1016/j.jinorgbio.2015.08.014

    5. [5]

      Yang, H.; Liu, Z.; Meng, Y.; Zeng, S.; Dou, J. A bell-like 15-metallacrown-5 complex from flexible H2glyha ligand: synthesis, structure and filed-induced slow magnetic relaxation. J. Mol. Struct. 2020, 1221, 128822‒128837. doi: 10.1016/j.molstruc.2020.128822

    6. [6]

      Wei, L. Q.; Li, B. W.; Hu, S.; Zeng, M. H. Controlled assemblies of hepta- and trideca-coii clusters by a rational derivation of salicylalde Schiff bases: microwave-assisted synthesis, crystal structures, ESI-MS solution analysis and magnetic properties. CrystEngComm. 2011, 13, 510‒516. doi: 10.1039/C0CE00085J

    7. [7]

      Mayans, J.; Font-Bardia, M.; Escuer, A. Triple halide bridges in chiral Mn2IIMn6IIINa2I cages: structural and magnetic characterization. Inorg. Chem. 2018, 57, 926‒929. doi: 10.1021/acs.inorgchem.7b03125

    8. [8]

      Yang, W.; Yang, H.; Zeng, S.; Li, D. C.; Dou, J. Unprecedented family of heterometallic LnIII[18-metallacrown-6] complexes: syntheses, structures, and magnetic properties. Dalton Trans. 2017, 46, 13027‒13034. doi: 10.1039/C7DT02735D

    9. [9]

      Zhang, Y.; Wu, J.; Shen, S.; Liu, Z.; Tang, J. Coupling Dy3 triangles into hexanuclear dysprosium(III) clusters: syntheses, structures and magnetic properties. Polyhedron 2018, 150, 40‒46. doi: 10.1016/j.poly.2018.04.042

    10. [10]

      Zou, H. H.; Wang, R.; Chen, Z. L.; Liu, D. C.; Liang, F. P. Series of edge-sharing bi-triangle Ln4 clusters with a µ4-NO3 bridge: syntheses, structures, luminescence, and the SMM behavior of the Dy4 analogue. Dalton Trans. 2014, 43, 2581‒2587. doi: 10.1039/C3DT52316K

    11. [11]

      Peng, Y.; Mereacre, V.; Baniodeh, A.; Lan, Y.; Schlageter, M.; Kostakis, G. E. Effect of ligand field tuning on the SMM behavior for three related alkoxide-bridged dysprosium dimers. Inorg. Chem. 2016, 55, 68‒74. doi: 10.1021/acs.inorgchem.5b01793

    12. [12]

      Lu, Z.; Fan, T.; Guo, W.; Lu, J.; Fan, C. Synthesis, structure and magnetism of three cubane Cu(II) and Ni(II) complexes based on flexible Schiff-base ligands. Inorg. Chim. Acta 2013, 400, 191‒196. doi: 10.1016/j.ica.2013.02.030

    13. [13]

      Wang, Y. N.; Zhang, P.; Yu, J. H.; Xu, J. Q. 4-(4-carboxyphenoxy)phthalate-based coordination polymers and their application in sensing nitrobenzene. Dalton Trans. 2015, 44, 1655‒1663. doi: 10.1039/C4DT02762K

    14. [14]

      Hoshino, N.; Ako, A. M.; Powell, A. K.; Oshio, H. Molecular magnets containing wheel motifs. Inorg. Chem. 2009, 48, 3396‒3407. doi: 10.1021/ic801776w

    15. [15]

      Chan, M. H. Y.; Leung, Y. L.; Yam, W. W. Controlling self-assembly mechanisms through rational molecular design in oligo(p-phen-yleneethynylene)-containing alkynylplatinum(II) 2, 6-bis(n-alkylbenzimidazol-2΄-yl)pyridine amphiphiles. J. Am. Chem. Soc. 2018, 140, 7637−7646. doi: 10.1021/jacs.8b03628

    16. [16]

      Sessoli, R.; Tsai, H. L.; Schake, A. R.; Wang, S.; Vincent, J. B.; Folting, K. High-spin molecules: [Mn12O12(O2Cr)16(H2O)4]. J. Am. Chem. Soc. 1993, 115, 1804−1816. doi: 10.1021/ja00058a027

    17. [17]

      Chow, C. Y.; Trivedi, E. R.; Pecoraro, V. L.; Zaleski, C. M. Heterometallic mixed 3d-4f metallacrowns: structural versatility, luminescence, and molecular magnetism. Comment Inorg. Chem. 2015, 35, 1−40. doi: 10.1080/02603594.2014.974805

    18. [18]

      Noord, C. V.; Kampf, J. W.; Pecoraro, V. L. Preparation of resolved fourfold symmetric amphiphilic helices using chiral metallacrown building blocks. Angew. Chem. Int. Ed. 2002, 41, 4667−70. doi: 10.1002/anie.200290010

    19. [19]

      Deng, M.; Yang, P.; Liu, X.; Xia, B.; Chen, Z.; Ling, Y. End-end connection pattern of trinuclear-triangular copper cluster for construction of two metal-organic frameworks: syntheses, structures, magnetic and gas adsorption properties. Cryst. Growth Des. 2015, 153, 5794−5799.

    20. [20]

      Xu, H. B.; Wang, B. W.; Pan, F.; Wang, Z. M.; Gao, S. Stringing oxo-centered trinuclear [Mn3IIIO] units into single-chain magnets with formate or azide linkers. Angew. Chem. Int. Ed. 2007, 119, 7532−7536. doi: 10.1002/ange.200702648

    21. [21]

      Lah, M. S.; Pecoraro, V. L. Isolation and characterization of {MnII[MnIII(salicylhydroximate)]4(acetate)2(DMF)6∙cntdot∙2DMF: an inorganic analog of M2+[12-crown-4]. J. Am. Chem. Soc. 1989, 111, 7258−7289. doi: 10.1021/ja00200a054

    22. [22]

      Cao, F.; Wang, S.; Li, D. Family of mixed 3d-4f dimeric 14-metallacrown-5 compounds: syntheses, structures, and magnetic properties. Inorg. Chem. 2013, 52, 10747−10755. doi: 10.1021/ic3025952

    23. [23]

      Nguyen, T. N.; Chow, C. Y.; Eliseeva, S. V.; Trivedi, E. R.; Kampf, J. W.; Martini, I. One-step assembly of visible and near-infrared emitting metallacrown dimers using a bifunctional linker. Chem. Eur. J. 2018, 24, 1031−1035. doi: 10.1002/chem.201703911

    24. [24]

      Woo, S. Y.; Mallah, T.; Pecoraro, V.; Kociak, M.; Zobelli, A. Luminescence from isolated Tb-based metallacrown molecular complexes on h -BN. Microsc. Microanal. 2019, 25, 604−605. doi: 10.1017/S1431927619003751

    25. [25]

      Muravyeva, M. S.; Zabrodina, G. S.; Samsonov, M. A.; Kluev, E. A.; Khrapichev, A. A.; Katkova, M. A.; Mukhina, I. V. Water-soluble tetraaqua Ln(III) glycinehydroximate 15-metallacrown-5 complexes towards potential MRI contrast agents for ultra-high magnetic field. Polyhedron 2016, 114, 165−171. doi: 10.1016/j.poly.2015.11.033

    26. [26]

      Chow, C. Y.; Guillot, R.; Rivière, E.; Kampf, J. W.; Pecoraro, V. L. Synthesis and magnetic characterization of Fe(III)-based 9-metallacrown-3 complexes which exhibit magnetorefrigerant properties. Inorg. Chem. 2016, 55, 10238–10247. doi: 10.1021/acs.inorgchem.6b01404

    27. [27]

      Happ, P.; Rentschler, E. Enforcement of a high-spin ground state for the first 3d heterometallic 12-metallacrown-4 complex. Dalton Trans. 2014, 43, 15308–15312. doi: 10.1039/C4DT02275K

    28. [28]

      Jin, C.; Yu, H.; Jin, L.; Wu, L.; Zhou, Z. Esterification and isolation of the carboxylic acid with salicyl-bis-hydrazide via coordination of iron(III) 18-metallacrown-6 complex. J. Coord. Chem. 2010, 63, 3772–3782. doi: 10.1080/00958972.2010.520706

    29. [29]

      Jin, C. Z.; Wu, S. X.; Jin, L. F.; Wu, L. M.; Zhang, J. Esterification of the ligand: synthesis, characterization and crystal structure of an iron(III) 18-metallacrown-6 complex with methyl 4-(5-chlorosalicylhydrazinocarbonyl) butyrate. Inorg. Chim. Acta 2012, 383, 20–25. doi: 10.1016/j.ica.2011.10.021

    30. [30]

      Thorarinsdottir, A. E.; Gaudette, A. I.; Harris, T. D. Spin-crossover and high-spin iron(II) complexes as chemical shift 19f magnetic resonance thermometers. Chem. Sci. 2017, 8, 2448–2456. doi: 10.1039/C6SC04287B

    31. [31]

      Phonsri, W.; Martinez, V.; Davies, C. G.; Jameson, G.; Moubaraki, B.; Murray, K. S. Ligand effects in a heteroleptic bis-tridentate iron(III) spin crossover complex showing a very high 1/2 value. Chem. Commun. 2016, 52, 1443–1446. doi: 10.1039/C5CC08701E

    32. [32]

      Sheldrick, G. M. A short history of SHELX. Acta Cryst. 2008, A64, 112‒122.

    33. [33]

      Alvarez, S.; Alemany, P.; Casanova, D.; Cirera, J.; Llunell, M.; Avnir, D. Shape maps and polyhedral interconversion paths in transition metal chemistry. Coord. Chem. Rev. 2005, 249, 1693–1708. doi: 10.1016/j.ccr.2005.03.031

    34. [34]

      Liu, W. T.; Thorp, H. H. Bond valence sum analysis of metal-ligand bond lengths in metalloenzymes and model complexes. 2. refined distances and other enzymes. Inorg. Chem. 1993, 32, 4102–4105. doi: 10.1021/ic00071a023

    35. [35]

      Yuan, A. H.; Lu, L. D.; Shen, X. P.; Chen, L. Z.; Yu, K. B. Synthesis, crystal structure and magnetic properties of a two-dimensional mixed-valence assembly [Fe(salen)]2[Fe(CN)5NO]. Transit. Metal Chem. 2003, 28, 163–167. doi: 10.1023/A:1022977403373

    36. [36]

      Chilton, N. F.; Anderson, R. P.; Turner, L. D.; Soncini, A.; Murray, K. S. PHI: a powerful new program for the analysis of anisotropic monomeric and exchange-coupled polynuclear d- and f-block complexes. J. Comput. Chem. 2013, 34, 1164–1175.

    37. [37]

      Widita, R.; Muhammady, S.; Prasetiyawati, R. D.; Marlina, R.; Darma, Y. Revisiting the structural, electronic, and magnetic properties of (LaO)MnAs: effect of hubbard correction and origin of mott-insulating behavior. ACS Omega. 2021, 6, 4440–4447. doi: 10.1021/acsomega.0c05889

  • Scheme 1  Syntheses of 1 and 2

    Figure 1  Molecular structures of (a) 1 and (b) 2

    Scheme 2  Coordination modes of L

    Figure 2  (a) A boat-like core with a hypothetical personrowing, (b) Analogous [8-MC-4] metallacrown-like motif

    Figure 3  (a) Intermolecular interactions of 1, π-π stacking interactions of (b) Cg4∙∙∙Cg8 and (c) Cg5∙∙∙Cg5, (d) 3D supramolecular structure of 1

    Figure 4  (a) Hydrogen bonds and (b) 3D supramolecular structure of 2

    Figure 5  Plots of χMT vs. T (a) and M/B vs. H/T (b) for 1; Plots of χMT vs. T (c) and M/B vs. H/T (d) for 2

    Figure 6  The ac susceptibility temperature dependent diagram at 2000 Oe field: plots of χ'M vs. T (a) and χ"M vs. T(b) of 1; plots of χ'M vs. T (c) and χ"M vs. T (d) of 2

    Table 1.  Crystal Data and Structure Refinement for 1 and 2

    Crystal data 1 2
    Empirical formula C51H59ClFe5N12NaO17 C53H65Fe5N12NaO18
    Formula weight 1449.79 1460.41
    Crystal system Triclinic Triclinic
    Space group P$ \overline 1 $ P$ \overline 1 $
    a (Å) 15.6357(1) 13.9367(1)
    b (Å) 16.5733(2) 14.5856(2)
    c (Å) 17.6867(1) 20.3766(4)
    α (º) 71.111(6) 80.084(7)
    β (º) 84.047(5) 74.149(7)
    γ (º) 71.735(6) 68.295(8)
    Volume (Å3) 4117.9(5) 3690.3(5)
    Z 2 2
    Dc (g/cm3) 1.169 1.314
    μ (Cu) (mm-1) 7.734 8.319
    λ (Å) 1.54184 1.54184
    F(000) 1486 1504
    Crystal size (mm) 0.120 × 0.110 × 0.100 0.130 × 0.120 × 0.110
    T (K) 293(2) 134(2)
    S 0.869 0.924
    Reflections collected 29458 27798
    R and wR (I > 2σ(I)) 0.0643, 0.1527 0.0703, 0.1532
    R and wR (all data) 0.1144, 0.2624 0.1334, 0.2743
    下载: 导出CSV

    Table 2.  Na and Fe Ion Coordination Configurations for 1 and 2

    Hexagon
    (D6h)
    Pentagonal
    pyramid (C5v)
    Octahedron
    (Oh)
    Trigonal prism
    (D3h)
    Johnson pentagonal pyramid J2 (C5v)
    1 Na(1) 23.40 5.08 20.16 7.43 8.17
    Fe(1) 29.98 22.16 1.24 10.81 25.72
    Fe(2) 33.01 28.36 0.27 15.92 31.56
    Fe(3) 32.36 27.79 0.34 15.07 30.99
    Fe(4) 33.62 24.46 1.88 11.75 27.89
    Fe(5) 32.31 26.30 1.37 14.92 29.24
    2 Na(1) 22.49 6.98 18.90 5.81 10.61
    Fe(1) 33.54 22.05 1.75 10.98 26.13
    Fe(2) 30.58 23.12 1.23 12.15 26.50
    Fe(3) 30.38 22.21 1.25 10.70 25.87
    Fe(4) 32.63 28.65 0.22 15.84 31.72
    Fe(5) 32.43 27.16 0.34 14.82 30.63
    下载: 导出CSV

    Table 3.  Bond Valence Calculations (BVS) for 1 and 2

    Atoms +2 +3
    1 Fe(1) 2.64 3.10
    Fe(3) 2.64 3.13
    Fe(4) 2.57 3.01
    Fe(5) 2.62 3.06
    2 Fe(1) 2.71 3.18
    Fe(2) 2.70 3.16
    Fe(3) 2.62 3.08
    Fe(5) 2.62 3.11
    下载: 导出CSV
  • 加载中
计量
  • PDF下载量:  0
  • 文章访问数:  51
  • HTML全文浏览量:  4
文章相关
  • 发布日期:  2022-03-01
  • 收稿日期:  2021-07-19
  • 接受日期:  2021-09-15
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章