Cube-like 12-MC-4 and Offset Stacked 10-MC-3 Metallacrowns: Synthesis, Structure, and Magnetic Properties

Article abstract of DOI:10.1002/zaac.201900014

Two complexes [Mn^III₄(naphthsao)₄(naphthsaoH)₄] (1) and [Fe^III₆O₂(naphthsao)₄(O₂CPh)₆] (2) [naphthsao = 1-(1-hydroxy-naphthalen-2-yl)ethanone oxi

Full text of DOI:10.1002/zaac.201900014

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201900014
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Cube-like 12-MC-4 and Offset Stacked 10-MC-3 Metallacrowns:
Synthesis, Structure, and Magnetic Properties
Jian-Hui Su,[a] Hua Yang,[a] Hai-quan Tian,[a] Da-Cheng Li,*[a] and Jian-Min Dou*[a]
Abstract. Two complexes [MnIII4(naphthsao)4(naphthsaoH)4] (1) and plays 12-MC-4 metallacrown structural type with cube-like configura-
[FeIII6O2(naphthsao)4(O2CPh)6] (2) [naphthsao = 1-(1-hydroxy-naph-
tion and 2 shows an offset stacked 10-MC-3 structural type with the
thalen-2-yl)ethanone oxime] were obtained through the reactions of
ring connectivity containing Fe–O–C–O–Fe–O–N–Fe–O–N. Magnetic
naphthsao ligand and MnCl2·4H2O or FeCl3·6H2O in the presence of susceptibility measurement reveals the ferromagnetic interactions and
triethylamine (Et3N). Their structures were determined by X-ray single field-induced slow relaxation of the magnetization for 1, whereas out-
crystal diffraction, elemental analysis, and IR spectra. Complex 1 dis- of-phase signal is not observed for 2.
MCs complexes usually possess different paramagnetic met-
Introduction
allic ions and small volume, thus, these features make MCs
Single molecule magnets (SMMs) have caused great atten-
present SMM behavior. Making the best of the small volume
tion due to the potential applications in the high density infor-
of MCs, the reactions of many paramagnetic metallic ions,
mation storage and quantum computing since the first SMM
such as MnIII, CoII, FeII, DyIII, TbIII, and hydroximic acid or
[Mn12] was discovered in 1990s.[1–7] Since then, many SMMs
sao ligands resulted into Mn–MCs, heterometallic 3d-4f MCs
have been designed and synthesized, for example, 3d-based
with different structural types. Due to the difference in struc-
SMMs, 3d/4f-based SMMs, and 4f-based SMMs according to
tures easily giving rise to the change of magnetic properties,
metal species. 3d-based SMMs mainly derived from Mn and
although MC complexes with SMM behavior have been re-
V complexes.[8–9] Because the ligand-field effect and structural
ported, it is still necessary to study the structure-magnetic
configuration play an important on the magnetic properties of
properties relationship of new MCs and enrich the magnetic
the complexes, it is still a great challenge for coordination
field.
chemists to synthesize new SMMs with the charming struc-
tures and properties.
The metallacrowns (MCs), a class of macrocyclic polynu-
So far, a large number of Mn MCs complexes have been
documented and the structures mainly exhibited conventional
structural types, such as the planar 9-MC-3, 12-MC-4, and
clear complexes, can be considered as the inorganic analogues
nonplanar 15-MC-5,[16] whereas for Fe MCs complexes, few
of organic crown ethers with methylene carbon atoms replaced
cases have been involved except the routine structural
by nitrogen atoms and metal ions in ring to exhibit M–N–O
types.[17] To obtain new type MCs complexes and expand the
connectivity.[10–12] So far, based on the number of ring atoms
metallic ions of MC ring, and to further discuss the effect of
including total atoms and metal ions, MCs demonstrate various
new structure on magnetic properties, we reported two new
structural types, such as 8-MC-4, 9-MC-3, 10-MC-5, 12-MC-
3, 12-MC-4, 12-MC-6, 14-MC-7, 15-MC-5, 15-MC-6, 16-MC-
MCs complexes [MnIII4(naphthsao)4(naphthsaoH)4 (1) and
[FeIII6O2(naphthsao)4(O2CPh)6] (2). The former shows a cube-
4, 16-MC-8, 18-MC-6, 18-MC-9, 20-MC-10, 22-MC-11, 24-
like 12-MC-4 structure, whereas the latter display an offset
MC-6, 24-MC-12, 28-MC-14, 30-MC-10, 32-MC-8, 32-MC-
stacked 10-MC-3 structural type. Their magnetic properties
16, 36-MC-12, 36-MC-18, 40-MC-10, 48-MC-24, and 60-MC-
also were explored in detail.
20.[13] Interestingly, these structural types have the relationship
with the choice of ligands and metal ions. For example, the
Results and Discussion
benzene ring-based salicyladoxime (sao) or hydroxamic acid-
ligands are close to Mn ion,[14] whereas the pyridine-based
sao-ligands or aminhydroxamic acid ligands have a tendency
to Cu ions.[15] Therefore, it is important to choose the suitable
ligand to construct the expected structures and estimate their
properties.
The X-ray single-crystal structural analysis reveals that 1
crystallizes in the monoclinic space group C2/c and contains
two independent structural units (1a and 1b) with the two units
exhibiting similar molecular configuration (Figure 1). For 1a,
four Mn ions are hold together through eight ligands with four
doubly-deprotonated at the oxime oxygen and phenolic hy-
droxyl groups, displaying μ3-η2:η1:η1 (Scheme 1a) coordina-
tion fashion and four mono-deprotonated at phenolic hydroxyl
group, showing μ2-η1:η1 coordination fashion. With the bridg-
ing of oxime oxygen and nitrogen atoms, the molecule demon-
strates a 12-MC-4 metallacrown structural type but the metall-
* Prof. J. Dou
E-Mail: dougroup@163.com
[a] Shandong Provincial Key Laboratory of Chemical Energy Storage
and Novel Cell Technology
School of Chemistry and Chemical Engineering
Liaocheng University
252000, Liaocheng, P. R. China
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acrown ring occurs to distort badly. It is worth noting that the [Mn4] through nine C–H···π interactions and a π···π [(C37,
oxime oxygen atoms from four doubly-deprotonated ligands C38, C39, C40, C41, C46) (C145, C146, C147, C148, C149,
further link the adjacent Mn ions to complete double bridging C154)], π···π centroid 3.923 Å (Figure 2b).[19]
between two adjacent metal ions. Thus, 1a also displays an
analogous cube-like configuration with each face constituted
by pentagon.
Figure 2. Intramolecular interaction of complex 1 with hydrogen
bonding shown as dashed. Molecules of the same color are in the same
hydrogen-bonded channel.
Figure 1. The molecular structure of complex
1 (a, b) and
[Mn4(NO)4]+8 core.
The X-ray single-crystal structural analysis reveals that 2
crystallize in the monoclinic space group C2/c and the mol-
ecule consists of six Fe ions, four deprotonated ligands, six
benzoate anions, two coordinated ethanol molecules, and two
μ3-O2– anions (Figure 3). The structure is centrosymmetric and
contains a hexanuclear [Fe6(μ3-O)2]14+ core with an off-set 10-
MC-3 unit, in which two trinuclear subunits [Fe3(μ3-O)2]7+
were fused together through two naphthol O atoms (O4 and
O4a) and two ketnoe oxime O atoms (O13 and O13a). A sim-
ilar structure has been reported in the literature.[20] Four li-
gands adopt two coordinate motifs μ2-η1:η1:η1 and μ2-
η2:η1:η2 (Scheme 1c and d). Two ligands with μ2-η1:η1:η1 co-
ordinate motif link Fe2 and Fe3 (Fe2a and Fe3a) and two li-
gand bond Fe1, Fe3a, Fe1a and Fe3 through μ4-η2:η1:η2 coor-
dinate motif. The average Fe–O bond lengths are 1.929(2) Å
(Fe–μ3-Ohydroxo), 2.023(2) Å (Fe–Obenzoate), 2.038(2) Å (Fe–
Scheme 1. The coordination motifs of naphthsao ligand in complex 1
(a, b) and 2 (c, d).
In 1a, all MnIII ions adopt six-coordinate distorted octahe-
dral arrangements and N2O4 coordination sphere with six co-
ordination atoms from two hydroxyl oxygen atoms, two oxime
oxygen atoms and two oxime nitrogen atoms. The distances of
Mn···Mn are in range 3.550(1)–3.977(1) Å with the shortest
distance between Mn1 and Mn4, and the longest distance be-
tween Mn1 and Mn3, respectively. All Mn–O bond lengths are
in range of 1.879(6) Å to 2.306(6) Å and Mn–N bond lengths
are 1.98(7) to 2.279(8) Å in 1a. The +3 oxidation state of Mn
ions is confirmed by the combination of bond length consider-
ations (the presence of Jahn–Teller axes), charge balance con-
siderations and BVS. calculations.[18] Because 1b possesses
similar structure with 1a, the structural description of 1b is not
discussed. In 1b, the shortest distance is Mn5–Mn7 and the
longest distance is Mn7–Mn8. The ranges of Mn–O distances
are 1.884(6) to 2.260(6) Å and of Mn–N distances 1.983(7) to
2.254(8) Å.
O
keynoe), and 2.104(3) Å (Fe–Oethanol), respectively. The sim-
ilar coordination motifs have been also reported.[20] The Fe–N
bond lengths are 2.089(3) and 2.127(3) Å. Each Fe ion com-
pletes its six-coordinate configuration. Fe1 has NO5 donor
atoms with coordination atoms provided by two μ4-η2:η1:η2
ligands, two benzoate anions, and one μ3-O2–. Fe2 is sur-
rounded by one ligand, three benzoate anions, one ethanol
molecule, and one μ3-O2. Fe3 is coordinated with one benzoate
O atom, one μ3-O2, two naphthol O atoms, one ketone oxime
O atoms from μ4-η2:η1:η2 ligand and N from μ2-η1:η1:η1 li-
Because compound 1 shows two independent [Mn4](1a)
molecules, there are a lot of C–H···O and C–H···π intermolecu-
alr interactions. Interestingly, the [Mn4] unit has assembled
with four neighboring [Mn4]’ (1b) units by C–H···π interac-
tions [C2–H2]···π (C133, C134, C135, C136, C137, C142)
H···centroid 2.838 Å, C···centroid 3.682 Å, C–H···centroid
138°; [C48–H48]···π (C1, C2, C3, C4, C5, C10) H···centroid
2.874 Å, C···centroid 2.784 Å, C–H···centroid 174° and C–
H···O hydrogen bonds [C78–H78···O32, H···O 2.472 Å, C···O
3.175 Å, C–H···O 133°] forming an undulated net running
Figure 3. The molecular structure of complex 2 (left) and [Fe6(μ3-
(Figure 2a). The [Mn4]’ units have also assemble with four O)2(μ2-O2R)6]8+ core (right).
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gand. The intramolecular Fe···Fe distances are in range of consistent with antiferromagnetic exchange between the cen-
3.2214(7)–3.4141(8) Å and the Fe–O–Fe bond angles are in tral metal atoms.
range of 104.17(10)–116.14(18)°.
For probing the magnetic behavior of complex 1, the ac
The complex 2 forms a two-dimensional network structure magnetization susceptibilities were investigated under a zero
through C–H···π interactions [C59–H59]···π (C14, C20, C30, applied dc field at frequencies in the range of 100–779 Hz and
C41, C50, C39) with H···centroids 3.479 Å, C–H···centroid the temperature range 4–20 K (Figure 6). The data are profiled
˚
164 and π···π interactions [(C48, C26, C55, C58, C56, C57) as χMЈT (in-phase) vs. T and χMЈЈ (out-of-phase) vs. T (Fig-
(C57, C56, C58, C55, C26, C48)], π···π centroid 3.689 Å (Fig- ure 6 left). As temperature decreasing, the in-phase signal in-
ure 4).
creases, indicating the presence of a smaller S value than the
ground state.[21] The χMЈT curves were extrapolated to 0 K
from 5 K to get a value of 20 cm–3·mol–1 K, which was in
agreement with S = 6 Ϯ1 ground state. Both χMЈ and χMЈЈ
data show frequency dependence below 3 K, indicating SMM
behavior. Owing to the limit of the instrument, the maximum
signals of χMЈЈ were not probed below 1.8 K, thus, the energy
barrier (Ueff) and relaxation time (τ0) cannot be calculated by
the traditional Arrhenius equation.[22] Therefore, the energy
Ueff (0.3 K) and τ0 (3.7ϫ10–5 s) were deduced through Debye
mode (Figure 7 right).
Figure 4. Intramolecular interaction of complex 2 with hydrogen
bonding shown as dashed. Molecules of the same color are in the same
hydrogen-bonded channel.
Figure 6. The plots of in-of-phase (χMTЈ) and out-of-phase (χMЈЈ) sig-
nals in 0 Oe dc field for complex 1.
The variable-temperature magnetic susceptibilities of 1 and
2 were investigated in the temperature range 2–300 K
under dc = 1000 Oe. For complex 1, the χMT value is
10.8 cm3·K·mol–1 at 300 K, which is significantly lower than
the calculated spin-only value of 12 cm3·Kmol–1 for four high-
spin MnIII ions with g = 2.0 (Figure 5). In the range of 100–
300 K, the value keeps steady, below 100 K, it increases
rapidly to 17.5 cm3·K·mol–1 at 5 K, indicating the presence of
strong ferromagnetic interaction within the [Mn4] cluster.
For complex 2, the room temperature χMT value of
24.5 cm3·K·mol–1 is lower than that expected for six non-inter-
acting FeIII ions (26.25 cm3·K·mol–1). Upon cooling, the value
of χMT decreases to 1.36 cm3·K·mol–1 at 5 K. This behavior is
Figure 7. Plots of χMЈЈ vs. T at 1000 Oe dc field (left) and ln(χЈЈ/χЈ)
vs. T–1/K–1 (right) for complex 1.
Conclusions
Two complexes [MnIII4(naphthsao)4(naphthsaoH)4] (1) and
[FeIII6O2(naphthsao)4(O2CPh)6] (2) were synthesized by the
naphthsaoH2. Complexes 1 and 2 are both the distorted metall-
acrown by structure analysis. Magnetic susceptibilities show
the ferromagnetic interactions and field dependent slow mag-
netization relaxation in complex 1 and antiferromagnetic inter-
actions in complex 2.
Experimental Section
Materials and Physical Methods: All materials were analytical grade
Figure 5. The plots of χMT vs. T for complexes 1 and 2.
and used as purchased from commercial sources. Elemental analyses
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of C, H and N were carried out through an Elemental Vario EL ana-
(10 mL) /acetonitrile (10 mL) in the presence of triethylamine
lyzer. The IR spectra were recorded as KBr pallets on the Perkin– (0.03 mL, 0.25 mmol). The solution was stirred for 5 h at room tem-
Elmer Spectrum. The magnetic susceptibilities were measured on crys- perature and filtered. The filtrate was left undisturbed to allow slow
talline samples at the temperature range 1.8–300 K under an applied
evaporation of the solvent. Black single crystals suitable for X-ray
field of 1 KOe with a Quantum Design SQUID magnetometer MPMS- diffraction were obtained after three weeks. Yield: 40 mg, 32% (based
XL17. AC susceptibility measurements were investigated in a zero
applied dc field and 1000 Oe dc field for 1.
on Mn). Fe6N4O24C94H76: calcd. C 57.01; H 3.86; N 2.83%; found:
C 56.87; H 3.69; N 2.66%. IR (KBr): ν˜ = 3448 (s), 2925 (w), 1617
(w), 1594 (m), 1555 (m), 1522 (w), 1402 (s), 1342 (w), 1236 (w),
1236 (w), 1146 (w), 1025 (w), 941 (m), 822 (m), 744 (w), 721 (s),
672 (w), 615 (w), 474 (m) cm–1.
X-ray Crystallography: X-ray diffraction single-crystal data mea-
surement for 1 and 2 were performed with a Bruker Smart CCD area-
detector diffractometer (Mo-Kα radiation, λMo = 0.71073 Å) at room
temperature. The program SAINT was used for integration of the dif-
fraction profiles, and the semiempirical absorption corrections were
applied using SADABS.[23] All structures were solved by direct meth-
ods using SHELXS-97 and refined by full least-matrix least-squares
on all F2 data with SHELXS-97.[24]
Acknowledgements
We are grateful for the financial supports received from the National
Natural Science Foundation of China (Grants 21671093 and
21701078).
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting the de-
pository numbers CCDC-1863505 (1) and CCDC-1863506 (2)
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk).
Keywords: 1-(1-Hydroxy-naphthalen-2-yl)ethanone oxime;
Metalacrown; Iron; Manganese; Magnetic properties
References
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range of 1615–1630 cm–1. The 624 cm–1 was assigned to the vibration
absorption of the M–O bond. The 431 cm–1 was classified as the
stretching vibration absorption of M–N bond.
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Published Online: ᭿
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Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
J.-H. Su, H. Yang, H.-q. Tian, D.-C. Li,* J.-M. Dou* ..... 1–6
Cube-like 12-MC-4 and Offset Stacked 10-MC-3 Metalla-
crowns: Synthesis, Structure, and Magnetic Properties
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