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

1. INTRODUCTION

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 (Mn^III, Fe^III, Co^II)^[6-8] and lanthanide ions (Dy^III, Tb^III, Er^III)^{[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 Fe^III MCs have been reported with the structure Containing Fe^III[9-MC_FeN(shi)^III-3]^[26], Cu^II[12-MC_FeN(Shi)^III-4]^[27], [18-MC_Fe^III-6]^{[28, 29]}, and their magnetocaloric effect has been discussed in detail. The recent studies of molecular magnets showed that the high spin Fe^III 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 Fe^III 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.

2. EXPERIMENTAL

2.1 Materials and methods

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.

2.2 Synthesis of complex 1

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).

2.3 Synthesis of complex 2

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).

2.4 X-ray structure determination

X-ray diffraction data for 1 and 2 were obtained on anAgilent Xcalibur Eos Gemini CCD plate diffractometer equipped with graphite monochromatic CuKα 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 (CuKα) (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

3. RESULTS AND DISCUSSION

3.1 Synthesis and characterization

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

DownLoad: Full-Size Img PowerPoint

3.2 Crystal structure of 1

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 C_5v 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

DownLoad: Full-Size Img PowerPoint

Scheme 2

Scheme 2.  Coordination modes of L

DownLoad: Full-Size Img PowerPoint

Figure 2

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

DownLoad: Full-Size Img PowerPoint

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

DownLoad: Full-Size Img PowerPoint

3.3 Crystal structure of 2

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 D_3h 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

DownLoad: Full-Size Img PowerPoint

3.4 Magnetic properties

For 1 and 2, variable temperature magnetic susceptibilities (χ_MT) have been measured in the range of 1.8~300 K at 1000 Oe dc. The χ_MT 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 Fe^III (S = 5/2, g = 2) (Fig. 5(a) and 5(c)). As [Fe(CN)₅NO]^2- is diamagnetic, the exchange interaction between Fe^II and Fe^III 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 Fe^III 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 χ_MT vs. T (a) and M/Nμ_B vs. H/T (b) for 1; Plots of χ_MT vs. T (c) and M/Nμ_B vs. H/T (d) for 2

DownLoad: Full-Size Img PowerPoint

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

DownLoad: Full-Size Img PowerPoint

4. CONCLUSION

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.

References

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 Mn₂^IIMn₆^IIINa₂^I 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 Ln^III[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 [Mn₃^IIIO] 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 {Mn^II[Mn^III(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