NiII, MnII, and CoII Coordination Polymers with 1,4 ... - ACS Publications

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NiII, MnII and CoII coordination polymers with 1,4-naphthalenedicarboxylic acid exhibiting metamagnetic and antiferromagnetic behaviors Ya-Min LI, Xue-Fei Li, Ying-Ying Wu, Daniel L. Collins-Wildman, ShengMin Hu, Ying Liu, Hai-Yan Li, Xiao-Wei Zhao, Lin-Yu Jin, and Dong-Bin Dang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01346 • Publication Date (Web): 23 Oct 2018 Downloaded from http://pubs.acs.org on October 26, 2018

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Crystal Growth & Design

NiII, MnII and CoII coordination polymers with 1,4-naphthalenedicarboxylic acid exhibiting metamagnetic and antiferromagnetic behaviors Ya-Min Li,*,† Xue-Fei Li,† Ying-Ying Wu,† Daniel L. Collins-Wildman,†† Sheng-Min Hu,††† Ying Liu,† Hai-Yan Li,† Xiao-Wei Zhao,*,† Lin-Yu Jin,† and Dong-Bin Dang*,† †Henan

Key Laboratory of Polyoxometalate, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, PR China ††Department of Chemistry, Emory University, Atlanta, GA 30322, USA †††State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China

Dedicated to the 80th birthday of Professor Xin-Tao Wu _______________________________________________________________________________________________________________ ABSTRACT: Three novel compounds, [Ni4(1,4-ndc)3(OH)2(H2O)2∙2.5H2O]n (1), {[Mn2(1,4-ndc)2(OAc)](C5MIm)∙0.5H2O}n (2) and {[Co3(1,4ndc)4(H2O)4](C5MIm)2∙2H2O}n (3), were hydro/solvothermally prepared with the corresponding acetate, 1,4-H2ndc (1,4-H2ndc = 1,4-naphthalenedicarboxylic acid) and different auxiliaries such as C5MImBr (C5MImBr = 1-pentyl-3methylimidazolium bromide) or 2,4-diamino-6-methyl-1,3,5-triazine. Compound 1 composes of one three-dimensional network, where one rare nickel chain is constructed through NiII ions bridged by μ3-OH– groups, μ3-η2:η1 and μ2-η1:η1 carboxyl groups from 1,4-ndc2− groups as well as coordination water molecules. In compound 2, MnII ions are connected by μ4-η1:η1:η1:η1 1,4-ndc2− groups and μ2-η1:η1 acetate radicals, forming a 3D framework. For compound 3, a [Co3(CO2)4(H2O)4] unit is observed, which is further bridged by μ2-η1:η0:η1:η0 and μ4η1:η1:η1:η1 1,4-ndc2− groups, and ultimately results in forming a 3D structure. It demonstrates compounds 1−3 can be noted as pcu, lon and the highly connected bcu topologies by topology analysis, respectively. Thorough magnetic study of 1 reveals the metamagnetic behavior, mainly resulting from the unique 1D NiII chain. Comparatively, magnetic analyses of 2 and 3 suggest the presence of the antiferromagnetic interactions with the best fitting magnetic susceptibility data for 2 (J = −0.85 cm−1 and g = 2.1) at 10−300 K. solvent, pH, temperature, and metal-ligand ratio. For example, under similar conditions, small synthetic adjustments may produce very distinct frameworks and properties. Most synthetic strategies for fabricating these materials involve choosing the optimal bridging ligand, which enables magnetic interaction in addition to binding multiple paramagnetic metals with unusual coordination modes. Multifunctional carboxylic acids are often used as ligands for the generation of ferromagnetic, antiferromagnetic, and metamagnetic compounds.13−15 For example, 1,4-naphthalenedicarboxylic acid (1,4-H2ndc) is a commonly used linear rigid carboxylic acid ligand due to its strong coordination ability and flexible coordination modes (Scheme 1), which provide different magnetic exchange pathways.16−18 Previous studies of both of antiferromagnetic and ferromagnetic exchange interactions through the syn-syn and trans-syn conformations have been reported.19−21 Furthermore, aromatic groups can also help facilitate the exchange of spins between the metals of two different paramagnetic centers.22,23 The choice of paramagnetic transition metal is also an essential

■ INTRODUCTION Recently, coordination polymers (CPs), as potential molecular magnetic materials are becoming a rapidly expanding research domain primarily focused on the synthesis and design of magnetic molecular compounds. The tunable characteristics of these polymers make them attractive targets for use in new types of quantum computing, magnetic devices, magnetic refrigeration, and so on, due to their fascinating structural diversity.1−4 Compared to traditional solid state magnetic materials, molecular magnetic compounds not only benefit from lower density, good solubility and versatility, but they also possess advantageous characteristics for their use as single-chain magnets (SCMs) 5,6 or single-molecule magnets (SMMs)7–9. In addition, some novel and complicated phenomena have also been found in molecular magnetic materials, such as metamagnetic behavior, spin glass, and spin frustration.10−12 Despite this large body of research, the field still faces many challenges including optimization of synthetic parameters such as

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groups in compound 1. The characteristic spectra at 1414 and 1606 cm−1, 1407 and 1568 cm−1, 1414 and 1616 cm−1 come from νs and νas stretching vibrations of −O−C−O− moieties. Their purities were determined by PXRD at a range of 5−50 º (Figure S2). The experimental spectra fit the simulated PXRD patterns well, suggesting there is good phase purity. Any discrepancies in peak intensities between experimental and simulated data may arise from non-random orientation of crystallites during data collection. The thermal stabilities of compounds 1-3 were assessed with thermogravimetric analyses over a temperature range of 30 to 1000 ºC. Figure S3 shows that compounds 1–3 have high stability. The loss of waters of hydration results in the first step loss, while the second step loss at 380–451 ºC for 1, 305–507 ºC for 2 and 280–463 ºC for 3, corresponds to the release of the 1,4-ndc2− groups and C5MIm+ with the collapse of the skeleton. Structural Description. [Ni4(1,4-ndc)3(OH)2(H2O)2∙2.5H2O]n (1) Compound 1 falls within triclinic system and P-1 space group (Table S1). This features a 3D network through the connection of 1D NiII chains by 1,4-ndc2– ligands. Each Ni ion is treated as a divalent cation, and μ3-O atoms are treated as hydroxyl oxygens in light of BVS (bond valence sums) calculations and charge balance (Table S2).26 Figure 1 shows all NiII ions are bound to six oxygen atoms yielding slightly distorted [NiO6] octahedrons. Within this complex the four individual carboxyl-O of 1,4-ndc2− ligands provide the four equatorial oxygens for [Ni1O6] and [Ni3O6], while the axial oxygen ligands come from a water and hydroxide. In contrast, the coordination geometry of [Ni2O6]/[Ni4O6] is comprised of three O atoms (O1, O10, O11 for Ni2 and O5, O6, O7 for Ni4) from three 1,4-ndc2– groups, two O atoms from two shared μ3-hydroxyl radicals (O3, O4 for Ni2/Ni4) as well as one oxygen atom (O2WA for Ni2 and O1W for Ni4, A: –1+x, y, z) from aqua ligands. Moreover, four NiII ions are almost in the same plane with a deviation of 0.008 Å (Ni1…Ni2 3.53 Å, Ni1…Ni4 3.31 Å, Ni2…Ni3 3.28 Å, Ni3…Ni4 3.55 Å). The Ni–O distances are from 1.973(2)–2.204(3) Å, comparable to the values of the general nickel coordination polymers (Table S3).27 As seen in Figure 2a, shown down the c-axis, the NiII are bound by μ3-η2:η1, μ2-η1:η1 carboxyl groups, μ3-OH– groups, in addition to the coordinated water forming a rare 1D NiII chain, which is very different from previously reported compounds in the literature.28,29 As shown in Figure 2b, viewed down a-axis direction, five neighboring chains are connected via 1,4-ndc2− groups with various binding modes (Scheme 1c and Scheme 1d) , thus expanding into one three-dimensional configuration and the lattice water molecules filling (Figure S4). This can be further understood by using topological analysis. If single 1,4-ndc2− ligand along the b-axis direction and double 1,4-ndc2− ligands along the c-axis direction are regarded as connectors, and the tetranuclear NiII units are treated as six-connected nodes, one typical uninodal four-connected slightly distorted pcu topology could more simply represent the whole three-dimensional network, which has a point symbol of {412.63} (Figure 2c)30. [Mn2(1,4-ndc)2(OAc)](C5MIm)∙0.5(H2O)}n (2) Compound 2 falls within a monoclinic system and space group P21/c with 3D network comprising 1D Mn chain bridged by 1,4-ndc2– (Table S1). Using charge balance and BVS,26 each Mn ion is assigned as a

parameter as the main spin barrier influences the difficulty of both experimental and theoretical analysis. For this, the 3d metal ions are easier to study when compared with the 4d and 5d metal ions. To date some CP ligands similar to 1,4-H2ndc have successfully been prepared with 3d metal, which has generated some fascinating magnetic properties.18,23-25 Our group previously reported a bilayer triangular lattice with high spin frustration, made up of crown-like Co7 units.23 Based on the above reasons, we selected 1,4-H2ndc as the ligand to react with NiII, MnII or CoII salts, forming three novel CPs [Ni4(1,4-ndc)3(OH)2(H2O)2∙2.5H2O]n (1), {[Mn2(1,4ndc)2(OAc)](C5MIm)∙0.5H2O}n (2), and {[Co3(1,4ndc)4(H2O)4](C5MIm)2∙2H2O}n (3) (C5MImBr = 1-pentyl-3methylimidazolium bromide), of which compound 1 displays metamagnetic behavior and both compounds 2 and 3 exhibit the antiferromagnetic phenomena.

Scheme 1. Various binding modes for 1,4-ndc2–.

■ RESULTS AND DISCUSSION Synthesis. When 2,4-diamino-6-methyl-1,3,5-triazine (dmt) was adapted as auxiliary, compound 1 was prepared, where dmt as the solid base can release a small number of OH− group to adjust pH under hydrothermal condition. The MnII and CoII compounds with different structures have been reported by our group,23,24 which can be gained under the similar conditions. Replacement of dmt, triethylamine or NaOH solution was added to adjust pH, meanwhile [C5MIm]Br was adopted to supply with the cations, compounds 2 and 3 with different structures were achieved. IR Spectra, PXRD and Thermal Properties. As shown in IR spectra (Figure S1), the peak at 3433 cm−1 of 1 corresponds to an −OH stretch, which provides evidence for the presence of −OH


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Crystal Growth & Design (Scheme 1f), different from that in compound 2. As shown in Figure 3c, if one half of the adjacent MnII ions are considered as one four-coordinate node with the 1,4-ndc2− groups examined as linear connectors, the general framework may be simplified to one lon topology with the point symbol of {66},31 which is a representation of framework topology. {[Co3(1,4-ndc)4(H2O)4](C5MIm)2∙2H2O}n (3) The structural data reveals that compound 3 forms monoclinic crystals belonging to space group P21/c generating 3D networks built up from linear [Co3(CO2)4(H2O)2] SBUs bridged by 1,4-ndc2– ligands (Table S1). All the Co ions are assigned as +2 oxidation states based on balancing the charge and in agreement with the BVS values (Table S3).26 Every Co center has six ligands, four of which are carboxylate based with the remaining two coming from axial aqua ligands (Figure S7). This generates a [CoO6] with a distorted octahedral configuration containing Co–O separations of 2.047(2)-2.171(2) Å (Table S2). Co1 metal center is located at the inversion center, forming a linear [Co3(CO2)4(H2O)2] SBU by the connection of two bridging aqua ligands and four μ2-η1:η1 carboxyl groups with Co2 and Co2A (A: 1–x, 1–y, 1–z) (Co1...Co2 3.5516(6) Å). The three-dimensional network is constructed by every SBU connected with eight neighboring SBUs via 1,4-ndc2– ligands with various binding mode (Scheme 1a and Scheme 1c, Figure 4a and Figure 4b). C5MIm+ is filled in the threedimensional network by electrostatic interaction, in a similar fashion to compound 2 (Figure S8). From the view of topology, each trinuclear metal cluster coordinated to eight 1,4-ndc2– ligands, can be seen as an eight-connected node where the 1,4-ndc2– ligand acts as the linker. This simplifies the entire structure into an eight-connected single mode 3D network where the point symbol is {424.64}, which is a known typical bcu topological net (Figure 4c).32

Figure 1. The coordination geometry of tetranuclear NiII unit showing thermal ellipsoids with 50% probability in 1. Symmetry codes: A: –1+x, y, z.

cation (Table S2). Every MnII ion is bounded by six oxygen atoms, resulting in a [MnO6] octahedron (Figure S5). In [Mn1O6], six oxygen atoms coordinated to Mn1 come from four separate 1,4-ndc2– ligands (O4, O5, O7, O9) and one OAc– (O1A and O2A, A: 1–x, 1–y, 2–z). While six oxygen atoms around Mn2/Mn3 are from two different OAc– (O2A, O2C for Mn2 and O1, O1C for Mn3, C: 1+x, y, z) and four separate 1,4-ndc2– ligands (O3, O6, O3B, O6B for Mn2 and O8, O10, O8A, O10A for Mn3, B: 2–x, 1–y, 2–z). Mn2 and Mn3 are located on both sides of Mn1 with the distances of Mn1…Mn2 3.6925(3) Å, Mn1…Mn3 3.7704(3) Å and Mn–O 2.114(15)–2.313(16) Å (Table S3). Thus, the MnII centers are bound by μ2-η1:η1 carboxyl groups and μ3-η2:η2 OAc–, forming a wave-like one-dimensional chain (Figure 3a). Different from compound 1, every 1D chain is further linked by the adjacent four 1D chains via 1,4-ndc2− groups (Scheme 1c), expanding it into a 3D structure (Figure 3b) with C5MIm+ filled

Figure 3. (a) 1D chain of 2 shown down b-axis direction. (b) 3D network of 2 shown down the a-axis direction. (c) 3D lon topology framework.

Figure 2. (a) The 1D Ni(II) chain of 1 shown down the c-axis direction. (b) The 3D network of 1 shown down the a-axis direction. (c) 3D pcu topology framework.

by electrostatic interactions (Figure S6). In the reported compound [Mn(1,4-ndc)]n,25 MnII centers are bound by μ2-η1:η1 carboxyl moieties forming [Mn-μ-O2]n chains, and further constructing one 3D network with μ6-η1:η2:η1:η2 1,4-ndc2− ligands



Magnetic Properties. For compound 1, magnetizability measurements were taken under 1000 Oe field at temperatures ranging from 2–300 K. Figure 5a shows when the temperature lowers from room temperature to 50 K, χmT rises gradually from 6.64 cm3 mol−1 K to a maximum of 6.93 cm3 mol−1 K, higher than the expectation of four isolated NiII ions in an octahedral coordinated environment at room temperature,26 indicating the sample is slightly ferromagnetic. With further lowering of the temperature, it sharply drops to 1.29 cm3 mol−1 K (2 K), because of NiII zero-field splitting17 and intrachain antiferromagnetic coupling. The optimized θ = +2.77 K and a C = 6.57 cm3 mol−1 K are gained by the Curie-Weiss law from 50–300 K. This positive value of θ also suggests weak ferromagnetism exists within intrachain NiII centers. The above magnetic features are very similar to those of the reported [Ni3(OH)2(tp)2(H2O)4] in terms of metamagnetic behavior, which drove us to further explore the magnetic phenomena of compound 1.21 As expected, the plot of the isothermal magnetization M(H) to the field (H = 0–8 T) at 2 K shows a sigmoidal shape (Figure 5b). M increases smoothly till an inflection point is found with Hc of 4.2 T, shown by the plot of dM/dH (Figure 5b, inset). In addition, a non-negligible hysteresis loop is also observed. All of these features support the existence of metamagnetic behavior (Figure 5b, inset).33,34 The magnetization is not completely saturated at 8T, which is 7.25 Nβ, below the saturation of four NiII metal centers. In addition, the measurement magnetizations that were either zero-field-cooled (ZFCM) or field-cooled (FCM) were also carried out (200 Oe, 100 Oe) (Figure S9a). The slight divergence was observed below 10 K for the two kinds of field conditions curves, demonstrating that there is some remnant magnetization. As the susceptibility measurements show no χ̋ and χ peaks, this demonstrates that it is not dependent on the frequency (Figure S9b). The magnetic coupling exchange interactions between NiII centers mainly contain the following modes in compound 1 according to the literature29,35 (Figure S10): (i) Two μ3-OH– (O3, o4) and a carboxyl-O (O13, O14) as bridges link the NiII centers (Ni2–Ni4) with a Ni2–O3–Ni4 angle of 98.77(10) º and a Ni2– O4–Ni4 angle of 98.16(10) º, (Ni1B–Ni3 (B: 1+x, y, z)) with a Ni1B–O14–Ni3 angle of 95.77(8) º and a Ni1B–O13–Ni3 angle of 97.42(9) º, which mainly contribute to ferromagnetic coupling

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interactions; (ii) The NiII centers are connected by syn-syn carboxyl groups, μ3-OH– (Ni2–O3–Ni3, Ni3–O3–Ni4, Ni4–O4– Ni1 and Ni2–O4–Ni1) with angles in the range of 110.50(11)– 125.28(12) º and coordination waters (Ni4–O1W–Ni1B and Ni3A–O2W–Ni2 (B: 1+x, y, z)) with angles in the range of 120.24(11)–120.42(11) º, which can mediate antiferromagnetic coupling interactions. Magnetic susceptibilities were taken as a function of temperature from 2−300 K using 1000 Oe field for compounds 2 and 3. Figure 6a indicates χmT is 8.73 cm3 mol−1 K at 300 K, almost identical with the dimer MnII expectation.24 In concert with dropping temperatures, χmT reduces more rapidly till reaching a minimum (0.57 cm3 mol−1 K) at 2 K. Furthermore, the optimized θ = −32.53 K and C = 9.62 cm3 mol−1 K are gained by the CurieWeiss law for temperatures ranging from 20–300 K (Figure S11a). Both of them demonstrate the antiferromagnetic based exchange interactions from one MnII ion to another. Additionally, although the 1D chain is constructed through the dimer MnII units connected by carboxyl group, the magnetic orbitals rarely overlap between dimer MnII units; therefore, a Mn2 model may be adopted to fit the data which accounts for intramolecular interactions. The data from 10–300 K is fitted using the following Eq.:18 2𝑁𝑔2𝛽2 55𝑥30 + 30𝑥20 + 14𝑥12 + 5𝑥6 + 𝑥2 35 𝜒m = (1 ― 𝜌) + 𝜌 (1) 𝑘(𝑇 ― 𝜃) 11𝑥30 + 9𝑥20 + 7𝑥12 + 5𝑥6 + 3𝑥2 + 1 12

{

}

𝑥 = exp (𝐽 𝑘𝑇) (2) ρ and θ are the proportion for MnII paramagnetic impurities and the correction term containing interdimer interaction in the two equations, respectively. J represents the exchange interaction for the dinuclear units, and the N, k and β have their usual physical meanings. The spin Hamiltonian operator is H = −2JS1S2. Finally, an optimized fit of the above equations yielded with the agreement factor R = 2.5×10−4: θ = −27.83 K, ρ = 0.61, g = 2.1 and J = −0.85 cm−1. For compound 3, the experimental χmT is 11.5 cm3 mol−1 K at 300 K (Figure 6b), far higher than the expectation of three isolated CoII, which may be due to a substantial spin-orbital coupling from CoII centers.36,37 χmT gradually decreases to one minimum (2.3 cm3 mol−1 K,) as the temperature lowering to 2 K, indicating antiferromagnetic based interaction within linear {Co3}

Figure 4. (a) The linkages of trinuclear Co(II) cluster with eight neighboring cores in 3. (b) The 3D network of 3. (c) 3D bcu topology framework.


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Crystal Growth & Design

Figure 6. The χm/χmT vs. T curves ((a) for 2) and χmT/χm–1 vs. T curves ((b) for 3) from 2–300K under 1000 Oe. Solid red line corresponds to the optimized fitting.

Figure 5. (a) The χmT/χm–1 vs. T curves for compound 1 from 2–300 K (1000 Oe). Solid red line corresponds to the optimized fitting. (b) M vs. H plot (2.0 K). Inset: the plots of dM/dH vs. H. and magnetic hysteresis loop.

link 1D wave-like MnII chains, forming a 3D network with the typical lon-type topological structure. For compound 3, trinuclear [Co3(CO2)4(H2O)2] clusters are connected by μ4-η1:η1:η1:η1 and μ2η1:η0:η1:η0 1,4-ndc2− groups constructing a 3D architecture, simplified as the highly connected bcu topology. Thus, the three compounds display distinct magnetic behaviors with compound 1 showing metamagnetic behavior, while both compounds 2 and 3 exhibit antiferromagnetic behaviors.

unit bound via syn-syn O−C−O and μ2-H2O (the larger Co−O−Co angles 113.10(9) °).38,39 The optimized θ = −43.68 K and C = 13.13 cm3 mol−1 K are gained by the Curie-Weiss law for temperatures ranging from 40–300 K, which further reveals presence of antiferromagnetic interactions among neighboring CoII metal centers. The magnetization M(H) of compounds 2 and 3 were also measured as a means to examine magnetic properties at low temperatures (Figure S11b and Figure S12).

■ ASSOCIATED CONTENT

■ CONCLUSIONS

Supporting Information

In conclusion, three different configurations [Ni4(1,4ndc)3(OH)2(H2O)2∙2.5H2O]n (1), {[Mn2(1,4ndc)2(OAc)](C5MIm)∙0.5H2O}n (2) and {[Co3(1,4ndc)4(H2O)4](C5MIm)2∙2H2O}n (3) have successfully been synthesized with the assembly of 1,4-ndc2− groups with metal ions by selecting different auxiliaries under solvothermal conditions, where various coordination modes are adopted for 1,4-ndc2− ligands. For compound 1, the connection of rare 1D NiII chains with μ5-η1:η1:η2:η1 and μ4-η1:η1:η1:η1 1,4-ndc2− groups constructs a 3D network, where a pcu topology can simplify the entire structure. But in compound 2, only μ4-η1:η1:η1:η1 1,4-ndc2− groups

Experiment section, IR spectra, PXRD patterns, TG curves and related structural figures; Additional magnetic characterizations; Crystallographic, bond distances and angles, and BVS tables; Crystallographic data in CIF format (CCDC: 1843271–1843273). ■ AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected]. *E-mail: [email protected]. *E-mail: [email protected].



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■ ACKNOWLEDGEMENTS Financial support is from the Natural Science Foundation of China (U1504209, 21403053), Young Backbone Teacher Project of Henan Colleges and Universities (2016GGJS-023) and Foundation of Henan University (0000A40478).

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NiII, MnII and CoII coordination polymers with 1,4-naphthalenedicarboxylic acid exhibiting metamagnetic and antiferromagnetic behaviors Ya-Min Li,*,† Xue-Fei Li,† Ying-Ying Wu,† Sheng-Min Hu,†† Daniel L. Collins-Wildman,†† Ying Liu,† HaiYan Li,† Xiao-Wei Zhao,*,† Lin-Yu Jin,† and Dong-Bin Dang*,†

With 1,4-naphthalenedicarboxylic acid as the ligand, NiII, MnII and CoII coordination polymers were synthesized, exhibiting metamagnetic and antiferromagnetic behaviors.


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NiII, MnII, and CoII Coordination Polymers with 1,4 ... - ACS Publications

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