Alkylamine-Templated Niccolite Frameworks of - ACS Publications

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

Alkylamine-Templated Niccolite Frameworks of [GaIIIMII(HCOO)6]− (M = Fe, Ni): Structure, Magnetism, and Dielectricity Kai Wang,† Jian-Bo Xiong,† Bin Xia,† Qing-Lun Wang,*,† Yu-Zhang Tong,† Yue Ma,† Zhe-Ming Wang,*,‡ and Song Gao‡ †

College of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, People’s Republic of China ‡ College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, People’s Republic of China S Supporting Information *

ABSTRACT: The five heterometallic formate frameworks [EtA][GaIIIFeII(HCOO)6] (1; EtA = CH3CH2NH3+), [DMA][GaIIIFeII(HCOO)6] (2; DMA = (CH3)2NH2+), [DEtA][GaIIIFeII(HCOO)6] (3; DEtA = (CH3CH2)2NH2+), [MA][GaIIINiII(HCOO)6] (4; MA = CH3NH3+), and [DMA][GaIIINiII(HCOO)6] (5) were synthesized through solvothermal methods. Complexes 1−5 are isotructural, and all crystallize in the trigonal P31̅ c space group. Each metal center is 6-connected, with each HCOO− bridging ligand in an anti-anti mode to build a three-dimensional niccolite-like architecture. All of the complexes exhibit weak ferromagnetism at low temperature. A variable-temperature (VT) dielectric study indicates that the dielectric anomaly is induced by the freezing of motions from the protonated amines during the freezing process.

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INTRODUCTION Frameworks of metal formate with protonated amines as counterions are research focus due to phase transitions, novel structures and relevant properties such as magnetism, mechanical properties, luminescent properties, ferroelectricity properties and so on.1−6 Formate, as the smallest carboxylate bridging ligand, has little steric hindrance and can be used to construct multidimensional framework with various magnetic properties.7−10 Generally, the formate group can effectively transfer antiferromagnetic coupling between neighboring metal ions, leading to long-range magnetic ordering of ferrimagnetism or weak ferromagnetism.11,12 The early homometallic metal formates with formula [cat.][MII(HCOO)3] showed both magnetic and electric ordering simultaneously below a certain temperature and can exhibit multiferroic behavior.13−15 In recent years, heterometallic niccolite formate frameworks [cat.][MIIINII(HCOO)6] have become the focus of research because of the diversity in structures and properties.16−24 Most of them showed magnetic order, of which the Ni complex [(CH3)2NH2][FeIIINiII(HCOO)6] has the highest magnetic ordering temperature (42 K).23 The most important feature for metal formates with a niccolite structure is that they may © XXXX American Chemical Society

contain metal ions in two valence states, which would give rise to more complex and fascinating magnetic properties in comparison to those in the perovskites. For example, the complex [(CH3)2NH2][FeIIIFeII(HCOO)6] not only exhibits a negative magnetization value upon small field but also displays an unsymmetric magnetization reversal in the magnetic hysteresis.17 Recently, we reported the crystal structure, differential scanning calorimetry, and dielectric studies of four [GaMn(HCOO)6]− niccolite frameworks templated by various alkylamine cations.25 We developed a new strategy to modify the niccolite framework by introducing gallium(III) ions into this system. Following this line, we herein report five new complexes: [EtA][Ga I I I Fe I I (HCOO) 6 ] (1; EtA = CH3CH2NH3+), [DMA][GaIIIFeII(HCOO)6] (2; DMA = (CH3)2NH2+), [DEtA][Ga IIIFeII(HCOO)6] (3; DEtA = (CH3CH2)2NH2+), [MA][GaIIINiII(HCOO)6] (4; MA = CH3NH3+), and [DMA][GaIIINiII(HCOO)6] (5). Magnetic studies showed that complexes 1−5 all display spin-canting Received: January 14, 2018

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DOI: 10.1021/acs.inorgchem.8b00124 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

Figure 1. (a) Coordination environment of the (49·66) and (412·63) nodes in complexes 1−5. The pink trigonal prism shows the (49·66) nodes of MII, and the yellow octahedron shows the (412·63) nodes of GaIII. (b) (49·66)(412 ·63) topological view of 1−5. MII is shown in pink and GaIII in yellow. (c) View of the free cations of 1−5 filled in the cavities. MII is shown in pink, GaIII in yellow, O in red, and C in gray; blue circles represent the countercations (EtA+, DMA+, DEtA+, MA+). calorimeter with a high resolution of 0.4 μW. Nitrogen was the purging gas, and the heating/cooling rate was 5 K/min. The temperature-dependent dielectric constants were measured with a Tonghui TH2828A impedance analyzer with frequency ranging from 500 Hz to 1 MHz at a heating/cooling rate of 5 K min−1. X-ray Crystallography. Diffraction intensities for complexes 1−5 were collected on a computer-controlled Bruker SMART 1000 CCD diffractometer equipped with graphite-monochromated Mo Kα radiation (λ = 0.7107 Å) by using the ω-scan technique. Lorentz− polarization and absorption corrections were applied. Crystal structure data of both the high-temperature phase (293 K) and low-temperature phase (113 K) were solved by direct methods using the SHELXS program of the SHELXTL package and refined by full-matrix leastsquares methods with SHELXL.27 The non-hydrogen atoms were located in successive difference Fourier syntheses and refined with anisotropic thermal parameters on F2. Hydrogen atoms were generated theoretically and refined isotropically with fixed thermal factors. Crystal data and details of structural determination refinement of complexes 1−5 are given in Table S1. Selected bond lengths and angles are given in Table S2.

behavior. A variable-temperature (VT) dielectric study indicates that the dielectric anomaly is induced by the freezing of motions of the protonated amines during the freezing process.

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EXPERIMENTAL SECTION

Synthesis of [EtA][GaIIIFeII(HCOO)6] (1). Colorless crystals of 1 were synthesized by the solvothermal reaction of GaCl3 (2 mmol) and FeCl2·4H2O (2 mmol) in a mixed solution of N-ethylformamide and formic acid (total 12 mL) (1/1 v/v) at 140 °C for 2 days and then cooling to room temperature in 1 day. Yield: 50% (based on GaCl3). Anal. Calcd for C8H14NO12GaFe: C, 21.72; H, 3.16; N, 3.17. Found: C, 21.39; H, 2.83; N, 3.41. IR (KBr): 3108 s cm−1 for ν(N−H) and 1604 s cm−1 for ν(CO). Complexes 2 and 3 were synthesized by the same method as 1 using N,N-dimethylformamide (for 2) and N,N-diethylformamide (for 3) instead of N-ethylformamide. Anal. Calcd for C8H14NO12GaFe (2): C, 21.72; H, 3.16; N, 3.17. Found: C, 21.44; H, 2.93; N, 3.37. IR (KBr): 3112 s cm−1 for ν(N−H) and 1574 s cm−1 for ν(CO). Anal. Calcd for C10H18NO12GaFe (3): C, 25.54; H, 3.83; N, 2.98. Found: C, 26.04; H, 3.43; N, 3.13. IR (KBr): 3142 s cm−1 for ν(N−H) and 1572 s cm−1 for ν(CO). Synthesis of [MA][GaIIINiII(HCOO)6] (4). Green crystals of 4 were obtained in about 30% yield (based on GaCl3) through the solvothermal reaction of the mixture of GaCl3 (2 mmol) and NiCl2· 6H2O (2 mmol) in N-methylformamide and formic acid (total 12 mL) (1/1 v/v) at 140 °C for 2 days and then cooling to room temperature in 1 day. Anal. Calcd for C7H12NO12GaNi: C, 19.49; H, 2.78; N, 3.25. Found: C, 19.72; H, 3.04; N, 3.55. IR (KBr): 3092 s cm−1 for ν(N−H) and 1578 s cm−1 for ν(CO). Complex 5 was obtained by a method similar to that for 4 using N,N-dimethylformamide instead of N-methylformamide. Anal. Calcd for C8H14NO12GaNi: C, 21.57; H, 3.14; N, 3.14. Found: C, 21.28; H, 3.48; N, 3.44. IR (KBr): 3087 s cm−1 for ν(N−H) and 1610 s cm−1 for ν(CO). Physical Measurements. C, H, N elemental analyses were obtained by using a PerkinElmer Model 240C analyzer. The IR spectra were measured as KBr pellets on a Bruker Tensor 27 FTIR spectrophotometer in the of 4000−400 cm−1 region. The magnetic data were recorded on a Quantum Design MPMS-7 SQUID magnetometer on crystal samples for all five complexes. Diamagnetic corrections were done with Pascal’s constants for all of the constituent atoms.26 Heat capacity was determined using a Mettler Toledo DSC-1

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RESULTS AND DISCUSSION

Crystal Structures. Variable-temperature diffraction data indicate that complexes 1−5 all crystallize in the trigonal space group P31̅ c. No obvious phase transition can be found in these compounds above 110 K (Table S1 in the Supporting Information). Complexes 1−5 are isomorphic with the previously reported [DMA][MIIFeIII(HCOO)6] metal niccolite formates.17 They have a [GaIIIMII(HCOO)6]− skeleton with (412·63)(49·66) topology25 (M = Fe for 1−3 and M = Ni for 4 and 5); only the counterions are different. Therefore, only the crystal structure of complex 1 is discussed here. In the framework of 1, GaIII ions are located in (412·63) nodes and FeII ions are in (49·66) nodes. Both are 6-coordinated. GaIII ion links six FeII ions by six formate groups in an anti-anti mode to form an octahedron. FeII ion links six GaIII ions by six formates to become a trigonal prism. Two metal nodes are connected alternately so as to build a 3D niccolite framework (Figure 1). The intramolecular Fe···Ga distance through bridging formate is 5.860 Å, and the nearest Fe···Fe distance is 8.171 Å. The B


Article

Inorganic Chemistry GaIII−O bond length in 1 is 1.977(3) Å, whereas FeII−O bonds range from 2.112(3) to 2.114(3) Å (Table S2). The EtA cations in 1 stayed in the cages show 3-fold disordering. They have a 3-fold and 2-fold parallel as well as perpendicular arrangement to the c axis (Figure 2a), respectively. In a view

Figure 2. (a) Disordered EtA cations filled in the cavities of 1. (b) Disordered DMA cations filled in the cavities of 2 and 5. (c) Disordered DEtA cations filled in the cavities of 3. (d) Disordered MA cations filled in the cavities of 4.

along the c direction, the EtA counterions are close to FeII ions (Figure 1c), consistent with the D3h symmetry of EtA cations in previously reported niccolite formate structures.20 EtA cations form hydrogen bonds with the formate oxygen atoms (O1···N1 = 2.961 Å). Disorder configurations of guest cations in 2, 4, and 5 are similar to those of the EtA cations of 1: i.e., all of them possess D3h symmetry with different alkyl groups along the c axis (Figure 2a,d). Remarkably differently from 1, DEtA cations have a pseudo-D3 symmetry in 3 (Figure 2c). Magnetic Properties. The magnetic behaviors of complexes 1−5 are similar (Figures 3 and 4 and Figures S1−S4). Therefore, only complex 1 is described as the representative here. The magnetic susceptibility for complex 1 was measured at 2−300 K and is shown in Figure 3a, in which χM is the molar magnetic susceptibility per GaIIIFeII unit. The χMT value at 300 K (3.85 cm3 K mol−1) is much larger than the spin-only value of a Fe(II) center (3 cm3 K mol−1, S = 2), which can be attributed to spin−orbit coupling of FeII ions.17,28 Between 300 and 28 K, the χMT value decreases slowly to 2.97 cm3 K mol−1 as the temperature is decreased . A Curie−Weiss fitting to the data above 28 K gives C = 3.97 cm3 K mol−1 and Θ = −10.35 K. The negative Θ value indicates zero-field splitting and/or antiferromagnetic interaction between FeII spin centers. Between 28 and 10 K, the χMT value increases rapidly to a maximum value of 14.62 cm3 K mol−1 upon further cooling. Below 10 K, the χMT value decreases rapidly and reaches 4.81 cm3 K mol−1 at 2 K due to the field saturation effect. All of the results are characteristic 3D long-range ordering of antiferromagnetic interaction with spin-canting behavior. The M vs H plots rise up continually, and the effective moment reaches 2.76 μB at 70 kOe (Figure 3b), less than the saturation value of a high-spin FeII (4 μB for S = 2, g = 2), indicating the presence of significant anisotropy of FeII and/or antiferromagnetic ordering. Its magnetic loop has 1000 Oe coercivity and 0.25 μB remanence. According to the formula sin α = (Mw/Ms),29,30 the spin-canting angle α of 1 was estimated to be 3.6°. The ZFC (zero-field-cooled magnetization) and FC (field-cooled

Figure 3. (a) χMT vs T and χM−1 vs T plots of 1 under an applied field of 1000 Oe. (b) M vs H plot of 1 at 2 K.

magnetization) curves at 50 Oe indicate a bifurcation below 18 K (Figure 4a), confirming the appearance of long-range magnetic ordering below this temperature. ac magnetic susceptibility (10, 100, and 1000 Hz) was conducted with Hdc = 0 Oe and Hac = 3 Oe. Obvious peaks in both χ′M and χ″M curves are found at 18 K in Figure 4b. In general, complex 1 mainly exhibits weak ferromagnetism behavior of spin canting with a Néel temperature of 18 K. The magnetic loop of complex 2 at 2 K has 2000 Oe coercivity and 0.2 μB remanence (Figure S1b). Therefore, the spin-canting angle α of 2 was deduced to be 2.9°. For complexes 3−5, the ZFC and FC curves clearly indicate a bifurcation at low temperature (Figures S2c, S3c, and S4c), confirming the occurrence of long-range magnetic ordering. Whereas no observable hysteresis loop was found, no typical peaks can be observed in the in-phase ac magnetic susceptibility (χ′) and the out-of-phase magnetic susceptibility (χ″) values are almost zero in complexes 3−5 (Figures S2−S4). The spin-canting behavior is usually derived from the Dzyaloshinsky−Moriya interaction (antisymmetric exchange) and the magnetic anisotropy.31,32 In most cases, the antisymmetric exchange is the main reason for the canting of formate-bridged complexes due to the deficiency of the inversion center of the MIII-(μ2-HCOO)-NII unit. For complexes 1−5, since the GaIII ions are diamagnetic, the antisymmetric exchange between paramagnetic FeII or NiII ions through formate bridges should be very weak. Therefore, the single-ion magnetic anisotropy of FeII or NiII may be the key reason to the emergence of spin-canting behavior. Weak C


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Inorganic Chemistry

Figure 4. (a) ZFC/FC measurements under a 50 Oe field for 1. (b) Zero-field ac in-phase (χM′) and out-of-phase (χM″) susceptibility vs T at various frequencies for 1.

the theoretical value. A similar report for the trigonal disorder in [DMA][Mn(HCOO) 3 ] was 4.7 J mol −1 K −1.40 As investigated before, a small amount of residual entropy is certainly left over as a result of a phase transition which has relaxation behavior. Therefore, the smaller values of ΔS in comparison to the theoretical value imply that some residual entropy has indeed been left over,41 indicating the relaxor character for the phase transitions, which was also confirmed by dielectric studies. Dielectric Studies. Variable-temperature (VT) dielectric spectra of complexes 1−5 were measured from 120 to 270 K. They all display relaxor-like behaviors with dielectric relaxation and dielectric dispersion (Figure 6 and Figures S5−S7). The dielectric responses (ε′ and tan δ) of 2 and 5 strongly exhibit frequency dependence, and the tan δ vs T traces display a strong frequency (f) dispersion (Figure 6a,b). The tan δ peaks correspond to the fall in the ε′ traces because of the Kramers− Krönig relations, and tan δ peaks go steadily from high temperature and high frequency to low temperature and low frequency.36,42 The frequency vs peak temperature in tan δ for 2 and 5 can be fitted by the Arrhenius law, leading to Ea/kB values of 2.8 × 103 K (0.24 eV for 2) and 2.5 × 103 K (0.22 eV for 5) and τ0 values of 3.18 × 10−14 s (2) and 1.05 × 10−13 s (5) (Figure 6c), respectively. The activation energy value Ea is similar to that in [DMA][Zn(HCOO)3] (Ea = 0.24 eV).43 It is significant proof that the freezing of motions of the protonated amines during the cooling process can bring about the dielectric anomaly. In other words, the rotations of DMA cations at room temperature are unimpeded; however, this kind of reorientational motion gradually slows down with a decrease in temperature and DMA cations are finally randomly immobilized at low temperatures, resulting in static disorder.

superexchange through hydrogen bond and dipole−dipole interactions between neighboring FeII centers may also contribute to the weak ferromagnetic ordering.33−35 The magnetic phase transition temperature of complex 1 (EtAGaFe) containing diamagnetic gallium(III) ions (18 K) is significantly lower than that of analogous DMAFeFe (37 K), DMAFeMn (35 K), and DMAFeCo (32 K) complexes which have two different magnetic centers.17 DSC Measurements. The differential scanning calorimetry measurements reveal that no clear peak was found in complexes 1, 4, and 5. However, for 2 and 3, the DSC spectra exhibit reversible heat anomalies during cooling and heating processes at around 144 and 190 K, respectively (Figure 5). The changes

Figure 5. DSC cycles for complexes 1−5.

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in enthalpy ΔH and entropy ΔS were respectively ca. 294 J mol−1 and 2.1 J mol−1 K−1 for 2 and 627 J mol−1 and 3.3 J mol−1 K−1 for 3. According to the crystal structure, no typical phase transition in 2 and 3 was observed above 110 K. The DMA (2) and DEtA (3) cations show trigonal disorder in the HTP and do not lose 3-fold disordering in the LTP (110 K). Therefore, these complexes may experience glassy transitions and the lattice symmetry is not altered. In other words, the protonated amines froze in the lattice randomly at low temperature. Similar results have been reported in the literature.36,37 In an order−disorder transition process, ΔS = R ln(N),38,39 in which N is the site numbers of the disordered system. Thus, for a complete 3-fold order−disorder transition, the change in entropy is then deduced to be R ln 3 = 9.1 J mol−1 K−1. The actual values of ΔS are significantly less than

CONCLUSIONS Five new heterometallic formate frameworks, [EtA][GaIIIFeII(HCOO)6] (1; EtA = CH3CH2NH3+), [DMA][GaIIIFeII(HCOO)6] (2; DMA = (CH3)2NH2+), [DEtA][GaIIIFeII(HCOO)6] (3; DEtA = (CH3CH2)2NH2+), [MA][Ga I I I Ni I I (HCOO) 6 ] (4; MA = CH 3 NH 3 + ), and [DMA][GaIIINiII(HCOO)6] (5), crystallizing in a niccolitelike architecture have been synthesized. Magnetic studies indicate that complexes 1−5 all display spin-canting behavior. The dielectric studies and crystal structure have proven that the frameworks of complexes 1−5 are stable, and none of them undergo a crystal phase transition above 110 K. The lack of a typical structural phase transition in complexes 1−5 can be D


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Inorganic Chemistry

Figure 6. (a) Temperature-dependent traces of the dielectric permittivities for 2. (b) Temperature-dependent traces of the dielectric permittivities for 5. (c) Arrhenius plots for the dielectric relaxations for 2 and 5.

ascribed to the less pliable and flexible skeleton due to the presence of trivalent gallium ions. It is worth noting that the prepared isomorphic complexes 1−5 with various organic amine cations which have a [GaMII(HCOO)6]− (M = FeII, NiII) anion niccolite framework have not been reported before. To a certain extent, these compounds broaden the scope and functionalities of metal−formate frameworks and deepen the study of the properties of the niccolite formate system.

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ORCID

Qing-Lun Wang: 0000-0002-0983-6280 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the NNSF of China (21771111, 21601092, 21471084 and 21371104) and MOE Innovation Team (IRT13022) of China.

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ASSOCIATED CONTENT

S Supporting Information *

DEDICATION Dedicated to Professor Dai-Zheng Liao on the occasion of his 80th birthday.

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00124. Tables S1 and S2 and Figures S1−S7 as described in the text (PDF) Accession Codes

CCDC 1573078−1573087 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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REFERENCES

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Corresponding Authors

*E-mail for Q.-L.W.: [email protected]. *E-mail for Z.-M.W.: [email protected]. E


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