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Lanthanide contraction and anion-controlled structure diversity in two types of novel 3d-4f heterometallic coordination polymers: Crystal structure and magnetic properties
Accepted Manuscript Research paper Lanthanide contraction and anion-controlled structure diversity in two types of novel 3d-4f heterometallic coordination polymers: crystal structure and magnetic properties Gang Xiong, Dan Qi, Yongke He, Lixin You, Baoyi Ren, Yaguang Sun PII: DOI: Reference:
S0020-1693(18)31078-8 https://doi.org/10.1016/j.ica.2018.08.044 ICA 18444
To appear in:
Inorganica Chimica Acta
Received Date: Revised Date: Accepted Date:
13 July 2018 25 August 2018 25 August 2018
Please cite this article as: G. Xiong, D. Qi, Y. He, L. You, B. Ren, Y. Sun, Lanthanide contraction and anioncontrolled structure diversity in two types of novel 3d-4f heterometallic coordination polymers: crystal structure and magnetic properties, Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.08.044
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Lanthanide contraction and anion-controlled structure diversity in two types of novel 3d-4f heterometallic coordination polymers: crystal structure and magnetic properties Gang Xiong*, Dan Qi, Yongke He, Lixin You, Baoyi Ren, Yaguang Sun* The Key Laboratory of Inorganic Molecule-Based Chemistry of Liaoning Province, Shenyang University of
Chemical
Technology,
Shenyang,
110142,
China.
E-mail:
[email protected];
[email protected]
Abstract Solvothermal reactions of isonicotinic acid (HIN) with lanthanide nitrate and cuprous halide yielded seven three-dimensional (3D) 3d-4f heterometallic coordination polymers (HCPs). These HCPs are formulated as {[NH2(CH3)2]2LnCu2Br(IN)6∙(DMA)2}n (Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5)) and [LnCu(IN)4∙DMA]n (Ln=Er(6), Yb(7)). Compounds 1-5 possess anionic three-dimensional pillared-layer frameworks with pcu topology, while compounds 6-7 show a rare 3d-4f dia-type two-fold interpenetrating framework with one dimensional square channels with side length of about 9.0 Å along the a axis. Crystal structure analysis reveals that the structure diversity is attributed to the synergistic effect of lanthanide contraction and halide anions. In addition, the magnetic properties of 1, 3, 4 and 5 were investigated.
Keyword: 3d-4f heterometallic coordination polymers, Interpenetrating structure, Magnetic properties, Crystal structure.
1. Introduction In recent years, the rational design and construction of 3d–4f heterometallic coordination polymers (HCPs) have garnered a remarkable amount of research attention not only due to their fascinating architectures and topologies [1-5], but also for their rich applications such as magnetic behavior [6-7], luminescence [8-11] and bimetallic catalysis [12]. However, the construction of lanthanide–transition metal heterometallic coordination polymers with intriguing topologies is still a challenging task, owing to the fact that the structures of HCPs are very sensitive to the synthesis conditions, such as reaction temperature[13-14], anion and cation species [6], reactant ratio and solvent species [15] and so on [16]. Therefore, chemists always meticulously regulate the synthesis conditions to obtain the desired multifarious HCPs. Of course, sometimes structural changes of HCPs are induced by multiple factors,
while most of chemists focused on a single factor to regulate the structure changes of HCPs for simplifying synthesis processes [17]. Thus, it is of great scientific significance to enrich the structures of HCPs through the multiple regulations of the reaction conditions. We are interested in the coordination chemistry of isonicotinic acid (HIN), a linear ligand with N,Ocoordination sites for the construction of high dimensional 3d-4f HCPs [18-20]. Recently, we employed the HIN as ligand to assemble several series of three-dimensional 3d-4f HCPs, for example, the three – dimensional [Gd3Cu12I12(IN)9(DMF)4]n and [Gd4Cu4I3(CO3)2(IN)9(HIN)0.5(DMF)(H2O)]n ， exhibited excellent catalytic performance in the carboxylation reactions of CO2 with 14 kinds of terminal alkynes under 1 atm and mild conditions without any co-catalyst/additive [21]. In this research, we report seven three-dimensional Ln(III)-Cu(I) HCPs, namely {[NH2(CH3)2]2LnCu2Br(IN)6∙(DMA)2}n (Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5)), and [LnCu(IN)4∙DMA]n (Ln=Er(6), Yb(7)]. Single crystal X-ray diffraction reveals that they exhibit two types of structures, 1-5 are anionic three-dimensional pillared-layer frameworks with pcu topology, while 6-7 exhibit a rare 3d-4f dia-type two-fold interpenetrating frameworks. In addition, the magnetic properties of 1, 3, 4 and 5 were investigated.
2. Experimental section 2.1 Materials and methods. All of the reagent-grade reactants were commercially available and employed without further purification. The elemental analyses (C, H, and N) were carried out applying a Perkin-Elmer 240C elemental analyzer. The powder X-ray diffraction (PXRD) data were measured with a BRUKER D8 ADVANCE diffractometer using CuKα(λ = 1.542 Å). The IR spectras were recorded in the range 400– 4000 cm−1 with a Nicolet IR-408 spectrometer using KBr pellets. Thermogravimetric analyses (TGA) were performed with a NETZSCH TG 209 instrument in nitrogen atmosphere in the range of 30-800 °C at a heating rate of 10 °C·min–1. Design MPMS-7 SQUID magnetometer was used to measure the temperature - dependented magnetic susceptibilities. Diamagnetic corrections were applied using Pascal’s constants for all constituent atoms. 2.2 Syntheses of compounds 2.2.1 Synthesis of compounds 1-5, {[NH2(CH3)2]2LnCu2Br(IN)6∙(DMA)2}n (Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5)) A mixture of HIN (49.2 mg, 4 mmol), CuBr (57.4 mg, 0.4 mmol), Ln(NO3)3·6H2O (44.4 mg, 0.1 mmol for 1, 44.6 mg, 0.1 mmol for 2, 45.1 mg, 0.1 mmol for 3, 45.3 mg, 0.1 mmol for 4, 45.6 mg, 0.1 mmol for 5), DMA (10 mL) was stirred at room temperature for 30 min and sealed in a 23 mL Teflonlined autoclave. Subsequently, the resulting solution was heated to 140 °C under autogenous pressure in 30 min and kept the temperature constant for 96 h. Then the autoclave was allowed to cool naturally to room temperature. After washing with DMA several times, the yellow crystals were collected. The yield based on the rare earth nitrate: for 1: 77.5%; for 2: 52.0%; for 3: 88.9%；for 4: 49.8%; for 5: 41.8%. Elem. anal. calcd. For 1 (%): C, 32.51; H, 4.81; N, 10.53. Found: C, 32.43; H, 4.81; N, 10.52. 2 (%): C,
43.28; H, 4.81; N, 10.51. Found: C, 43.25; H, 4.80; N,10.43. 3 (%): C, 43.11; H, 4.79; N, 10.48. Found: C, 43.06; H, 4.64; N, 10.32. 4 (%): C, 43.05; H, 5.62; N, 12.30. Found: C, 43.03; H, 5.60; N, 12.27. 5 (%): C, 42.93; H, 4.77; N, 10.44. Found: C, 42.85; H, 4.68; N, 10.32. 2.2.2 Synthesis of compounds 6-7, [LnCu(IN)4∙DMA]n (Ln=Er(6), Yb(7)]. A mixture of HIN (49.2 mg，4 mmol), CuCl (39.6 mg, 0.4 mmol), Ln(NO3)3·6H2O (46.1 mg, 0.1 mmol for 6; 46.7 mg, 0.1 mmol for 7), DMA (10 mL) was stirred at room temperature for 30 min and sealed in a 23 mL Teflon-lined autoclave. Subsequently, the autoclave was heated to 140 °C under autogenous pressure in 30 min and kept the temperature constant for 96 h. Then it was allowed to cool naturally to room temperature. After washing with DMA several times, the yellow crystals were collected. The yield based on the rare earth nitrate: for 6: 78.8%; for 7: 75.7%. Elem. anal. calcd. For 6 (%): C, 41.71; H, 3.10; N, 8.69. Found: C, 41.69 ; H, 3.08; N, 8.68. 7 (%): C, 41.41; H, 3.08; N, 8.63. Found: C, 41.39 ; H, 3.08; N, 8.62. 2.3 X-ray Crystallography All data collections were carried out at 293 K on a Rigaku XtaLABmini diffractometer with MoKα monochromated radiation (λ = 0.71073 Å) using the ω–2θ scan technique. Absorption corrections were performed by the CrystalClear program. Using Olex2 [22], the structure was solved by the ShelXS structure solution program [23], and refined with the ShelXL refinement package [24] using Least Squares minimisation. All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were riding on carbon atoms geometrically. Detailed crystallographic data and structure refinement parameters of 1-7 are summarized in Table S1. CCDC numbers for 1-7: 1853409-1853415
3 Results and discussion 3.1 Structure description 3.1.1. Crystal structures of 1-5 Single crystal X-ray diffraction analysis revealed that 1-5 crystallize in the I2/a space group, monoclinic system. Because 1-5 are isostructural, only the structure of compound 4 is described in detail. Fig. 1(a) presents a perspective view of the basic unit in 4 together with atomic labeling system. The asymmetric unit of complex 4 contains half Tb(Ⅲ) ion, one Cu (Ⅰ) ion, half Br(Ⅰ) ion, three IN anions, one protonated dimethylamine and one lattice DMA molecule. The Tb-O bond lengths are ranging from 2.276 to 2.572 Å which are comparable to those reported for the other Tb(Ⅲ) compounds [25-26]. The Tb(III) cation is coordinated with four monodentate carboxyl group oxygen atoms (O1, O3, O1A and O3A) from four IN anions and four chelated carboxyl group oxygen atoms (O5, O6, O5A and O6A) from two IN anions to form an extremely distorted {TbO8} dodecahedronal geometry. As far as the coordination geometric configuration of the Cu(Ⅰ) ion is concerned, it exhibits a tetrahedral geometry, being coordinated by one Br(Ⅰ) and three nitrogen atoms (N1B, N2B and N3) from the three IN anions. Two metal ions, Tb(III) and Cu(I), are connected through the terminal carboxylate and pyridine nitrogen
of the IN ligand end to end, forming a two-dimensional layer in the bc plane (Fig 1 (b)). The Br anion was coordinated with two Cu(I) cations from adjacent two dimensional layers (Fig. S1). As a result, the two-dimensional layers were linked via Br(Ⅰ) to form a three dimensional framework (Fig. 1(c)). Meanwhile, the protonated dimethylamines are connected with the coordinating carboxylate oxygen atoms (O2, O4) through N−H⋯O hydrogen bonding to keep the stability of the whole structure [27] (Fig. S2). Lattice DMA molecules also filled in the void of the three dimensional pillared-layer framework. Using the TOPOS 4.0 program, the Tb cations and Cu2Br units both can be regarded as 6-c nodals, the IN anions can be considered as linear. So the structure of compound 4 can be described as a pcu-type framework (Fig. 2).
Fig. 1. (a) The coordination environments of Tb(III) and Cu(I) ions of 4 drawn with the thermal ellipsoid probability of 30%. Symm. op.: A= -x, y, -0.5-z; B=x, -1+y, z; (b) View of the 2D layer; (c) View of the 3D pillared-layer structure of 4.
Fig. 2. The topology framework of 4. The purple balls represent the Tb(III) center and the green balls represent Cu2Br unit. 3.1.2. Crystal structures of 6-7 Single crystal X-ray diffraction analysis revealed that 6 crystallized in the orthorhombic system, Fdd2 space group, while 7 crystallized in the orthorhombic system, Fddd space group. However, they exhibited the same three-dimensional structures and topological structures after justifying from a careful structural analysis and the similar cell parameters presented in Table S1 of 6 and 7. The different space groups of 6 and 7 were caused by different orientations. [28] So only the structure of 7 is described in detail. The asymmetric unit contains 0.25 Yb (III) metal ion, 0.25 Cu (I) ion, one IN cation. Yb(III) was located in the center of an eight-coordinated distorted dodecahedron constructed by eight carboxyl oxygen atoms from four chelating carboxyl groups of four IN anions (Fig. 3). Yb-O bond lengths are 2.333(7) and 2.334(7)Å. Cu(I) was coordinated with four pyridine nitrogen atoms from four IN anions to assemble a perfect tetrahedral geometric configuration. The Cu-N bond length is 2.047(9)Å (Fig. 3). Actually, Yb(III) cations can be considered as tetrahedron tetrapod nodes. Each Yb(III) tetrahedron tetrapod node connected with four Cu(I) via IN anions to build up a dia framework. Two sets of dia frameworks further assemble to two-interpenetration dia framework with a channel side length of about 9.0 Å along the a axis for increasing the stability (Fig. 4). For 4-connected networks, the number of dia nets [29-30] is much bigger than those of the other well-known four-connected nbo [31] and sra [32], lvt nets [14]. Therefore, the number of interpenetrating dia frameworks is huge. To the best of our knowledge, the vast majority of interpenetrating dia are concentrated in transition metal coordination polymers, while the interpenetrating dia 3d-4f HPCs being similar to compound 7 are still very rare [34]. The channels were occupied by lattice DMA molecules. On the assumption of moving the free DMA molecules, the total potential accessible void is 2829 Å3 calculated by PLATON program [34], which is 40 % of cell total volume (7068 Å3). From the experimental conditions, the difference between compounds 1-5 and compounds 6 and 7 is the change of cuprous salt and rare earth salt, resulting in obvious structural changes. On the one hand,
the Br anion from the CuBr salt remained in the compounds 1-5, while the Cl anion from CuCl was not found in compounds 6 and 7. According to the theory of hard and soft acids and bases, the Br anion is a softer base than the Cl anion, the Cu(I) cation is a classic soft acid, therefore the Br anion was coordinated with a Cu(I) cation in compounds 1-5, while the coordinated sites of the Cu(I) cation were occupied by pyridine nitrogen atoms, which are softer than the Cl anion, in compounds 6 and 7. Thus, the secondary building units constructed by the Cu cations in compounds 1-5 were different from those in compounds 6 and 7. On the other hand, medium rare earth elements were employed in compounds 1-5, while heavy rare earth elements were used in the synthesis procedure of compounds 6 and 7. The ionic radius of medium rare earth elements is bigger than that of heavy rare earth elements due to effects of the lanthanide contraction. As a result, the secondary building units constructed by medium rare earth elements in compounds 1-5 were different from those in compounds 6 and 7. Consequentially, the structures of compounds 1-5 are completely different from the structures of compounds 6 and 7. Of course, this is exactly what we expect.
Fig. 3. The coordination environments of Yb(III) and Cu(I) cations in 7 drawn with the thermal ellipsoid probability of 30%. Symm. op.: A= 0.75-x, y, 0.75-z; B= x, 0.75-y, 0.75-z;C= 0.75-x, 0.75-y, z; D= 25-x, y, 1.25-z, E= 1.25-y, 1.25-z; F= 0.25-x, 1.25-y, z.
Fig. 4. (a) 3D two-fold interpenetrating framework of 7; (b) 3D two-fold dia interpenetrating topology of 7. 3.2. PXRD analysis, IR Spectroscopy and TGA analysis Powder X-ray diffraction (PXRD) analyses of compounds 1-7 were performed at room temperature (Fig. S3). The patterns for 1-7 were in good agreement with the simulated patterns obtained from the corresponding the single-crystal structures, confirming that the single-crystal structures are really representative for the corresponding powder samples. The FT-IR spectra of 1–7 were depicted in Fig. S4. The strong adsorption peaks in the region 1643cm-1-1542 cm-1 and 1415 cm-1-1387cm-1 are attributed to the symmetric stretching vibrations of carboxylic groups. The absence of strong bands in the range of 1690 cm-1-1730 cm-1 indicates that all carboxyl groups of HIN are deprotonated [35]. To study the thermal stability, thermogravimetric analyses of 1-7 were performed from 40 to 800 °C at a heating rate of 10 °C/min under N2 ambient. For compounds 1-5, the TGA curves are similar, compound 5 has been chosen for a detailed description. The first weight loss from 140 to 240°C corresponds to the loss of the protonated dimethylamine and lattice DMA molecules. Above 300℃, the framework gradually began to break down, the weight loss could be attributed to the decomposition of the organic ligands. For compounds 6-7, the TGA curves are roughly the same, the compound 6 is described. The first loss weight occurred about 100 to 200 ℃, corresponding to one free DMA molecule per formula, which can be confirmed via single crystal structure of the isostructural compound 7. Above 250 ℃, the structure started to decompose. The TGA results show that compounds 1-7 exhibited relatively good steady behavior. 3.3 Magnetic properties for 1, 3, 4 and 5 The magnetic susceptibility data of 1, 3, 4 and 5 were measured in the temperature range from 2 to 300 K under a 1000 Oe field, and χMT is shown in Fig. 5. For 1, the χMT value was 0.092 cm3 K mol-1 at 300 K, which was very close to the theoretical value of 0.090 cm3 K mol-1 based upon one Sm(III) ion
in the 6H5/2 ground state (g = 2/7). With decreasing temperature, the χMT value rapidly declined to a minimum of 0.035 cm3 K mol-1 at 2 K in a nearly linear relation, this maybe indicates very weak antiferromagnetic interactions between the adjacent Sm(III) ions [9]. For 3, 4 and 5, the χMT values were respectively 7.76 cm3 K mol-1, 14.26 cm3 K mol-1 and 14.03 cm3 K mol-1 at 300 K, which approaches the theoretical values of 7.88 cm3 K mol-1, 14.17 cm3 K mol-1 and 14.07 cm3 K mol-1, which were calculated based upon one Gd(III) ion in the 8S7/2 ground state (g = 2), one Tb(III) ion in the 7F6 ground state (g = 3/2), one Dy(III) ion in the 6H15/2 ground state (g = 4/3), respectively. As decreasing the temperature, the χMT values of 3, 4 and 5 decreased. Finally, the χMT value decreased to the minimum value of 6.66 cm3 K mol-1, 12.03 cm3 K mol-1 and 10.35 cm3 K mol-1 at 2K, respectively. The χMT vs. T plots of 3, 4 and 5 obey the Curie-Weiss law 1/χM = (T - θ)/C, corresponding to Curie constants C = 7.69 cm3 K mol-1, 14.26 cm3 K mol-1 and 14.30 cm3 K mol-1, and Weiss constants θ = -0.70 K, -0.65 K and -1.58 K, respectively. For 3, the trend of the χMT value and the negative value of θ indicated the existence of antiferromagnetic coupling between two Gd(III) ions [7,9]. For 4 and 5, however, the change trends of the χMT values with temperature and the negative θ value cannot unambiguously confirm antiferromagnetic coupling between two adjacent Tb(III) /Dy(III) ions because of depopulation of Stark sublevels of Tb(III) /Dy(III) can lead to decline of χMT value as lowering the temperature [7,9].
Fig. 5. Plots of χMT vs. T and χM–1 vs. T of 1, 3, 4 and 5.
4. Conclusion In summary, we have successfully synthesized seven novel 3D 3d-4f coordination polymers. Among
these compounds, 1-5 exhibited anionic three-dimensional pillared-layer frameworks with pcu topology, while 6-7 presented a rare 3d-4f two-fold interpenetrating dia-type framework. In addition, the magnetic property studies of 1, 3, 4 and 5 indicated superparamagnetic behavior.
Acknowledgements This work was supported by National Natural Science Foundation of China (21501122, 21701116 and 21671139), and the Doctoral Scientific Research Foundation of Liaoning Province (201601193). The Distinguished Professor Project of Liaoning Province (No. 2013204)
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Highlights
Two series of Ln- Cu HCPs were synthesized via tuning the CuX and lanthanum cations.
These HCPs exhibited different 3D framework.
The magnetic properties of 1, 3, 4 and 5 were investigated.
Graphical abstract
S0020-1693(18)31078-8 https://doi.org/10.1016/j.ica.2018.08.044 ICA 18444
To appear in:
Inorganica Chimica Acta
Received Date: Revised Date: Accepted Date:
13 July 2018 25 August 2018 25 August 2018
Please cite this article as: G. Xiong, D. Qi, Y. He, L. You, B. Ren, Y. Sun, Lanthanide contraction and anioncontrolled structure diversity in two types of novel 3d-4f heterometallic coordination polymers: crystal structure and magnetic properties, Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.08.044
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Lanthanide contraction and anion-controlled structure diversity in two types of novel 3d-4f heterometallic coordination polymers: crystal structure and magnetic properties Gang Xiong*, Dan Qi, Yongke He, Lixin You, Baoyi Ren, Yaguang Sun* The Key Laboratory of Inorganic Molecule-Based Chemistry of Liaoning Province, Shenyang University of
Chemical
Technology,
Shenyang,
110142,
China.
E-mail:
[email protected];
[email protected]
Abstract Solvothermal reactions of isonicotinic acid (HIN) with lanthanide nitrate and cuprous halide yielded seven three-dimensional (3D) 3d-4f heterometallic coordination polymers (HCPs). These HCPs are formulated as {[NH2(CH3)2]2LnCu2Br(IN)6∙(DMA)2}n (Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5)) and [LnCu(IN)4∙DMA]n (Ln=Er(6), Yb(7)). Compounds 1-5 possess anionic three-dimensional pillared-layer frameworks with pcu topology, while compounds 6-7 show a rare 3d-4f dia-type two-fold interpenetrating framework with one dimensional square channels with side length of about 9.0 Å along the a axis. Crystal structure analysis reveals that the structure diversity is attributed to the synergistic effect of lanthanide contraction and halide anions. In addition, the magnetic properties of 1, 3, 4 and 5 were investigated.
Keyword: 3d-4f heterometallic coordination polymers, Interpenetrating structure, Magnetic properties, Crystal structure.
1. Introduction In recent years, the rational design and construction of 3d–4f heterometallic coordination polymers (HCPs) have garnered a remarkable amount of research attention not only due to their fascinating architectures and topologies [1-5], but also for their rich applications such as magnetic behavior [6-7], luminescence [8-11] and bimetallic catalysis [12]. However, the construction of lanthanide–transition metal heterometallic coordination polymers with intriguing topologies is still a challenging task, owing to the fact that the structures of HCPs are very sensitive to the synthesis conditions, such as reaction temperature[13-14], anion and cation species [6], reactant ratio and solvent species [15] and so on [16]. Therefore, chemists always meticulously regulate the synthesis conditions to obtain the desired multifarious HCPs. Of course, sometimes structural changes of HCPs are induced by multiple factors,
while most of chemists focused on a single factor to regulate the structure changes of HCPs for simplifying synthesis processes [17]. Thus, it is of great scientific significance to enrich the structures of HCPs through the multiple regulations of the reaction conditions. We are interested in the coordination chemistry of isonicotinic acid (HIN), a linear ligand with N,Ocoordination sites for the construction of high dimensional 3d-4f HCPs [18-20]. Recently, we employed the HIN as ligand to assemble several series of three-dimensional 3d-4f HCPs, for example, the three – dimensional [Gd3Cu12I12(IN)9(DMF)4]n and [Gd4Cu4I3(CO3)2(IN)9(HIN)0.5(DMF)(H2O)]n ， exhibited excellent catalytic performance in the carboxylation reactions of CO2 with 14 kinds of terminal alkynes under 1 atm and mild conditions without any co-catalyst/additive [21]. In this research, we report seven three-dimensional Ln(III)-Cu(I) HCPs, namely {[NH2(CH3)2]2LnCu2Br(IN)6∙(DMA)2}n (Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5)), and [LnCu(IN)4∙DMA]n (Ln=Er(6), Yb(7)]. Single crystal X-ray diffraction reveals that they exhibit two types of structures, 1-5 are anionic three-dimensional pillared-layer frameworks with pcu topology, while 6-7 exhibit a rare 3d-4f dia-type two-fold interpenetrating frameworks. In addition, the magnetic properties of 1, 3, 4 and 5 were investigated.
2. Experimental section 2.1 Materials and methods. All of the reagent-grade reactants were commercially available and employed without further purification. The elemental analyses (C, H, and N) were carried out applying a Perkin-Elmer 240C elemental analyzer. The powder X-ray diffraction (PXRD) data were measured with a BRUKER D8 ADVANCE diffractometer using CuKα(λ = 1.542 Å). The IR spectras were recorded in the range 400– 4000 cm−1 with a Nicolet IR-408 spectrometer using KBr pellets. Thermogravimetric analyses (TGA) were performed with a NETZSCH TG 209 instrument in nitrogen atmosphere in the range of 30-800 °C at a heating rate of 10 °C·min–1. Design MPMS-7 SQUID magnetometer was used to measure the temperature - dependented magnetic susceptibilities. Diamagnetic corrections were applied using Pascal’s constants for all constituent atoms. 2.2 Syntheses of compounds 2.2.1 Synthesis of compounds 1-5, {[NH2(CH3)2]2LnCu2Br(IN)6∙(DMA)2}n (Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5)) A mixture of HIN (49.2 mg, 4 mmol), CuBr (57.4 mg, 0.4 mmol), Ln(NO3)3·6H2O (44.4 mg, 0.1 mmol for 1, 44.6 mg, 0.1 mmol for 2, 45.1 mg, 0.1 mmol for 3, 45.3 mg, 0.1 mmol for 4, 45.6 mg, 0.1 mmol for 5), DMA (10 mL) was stirred at room temperature for 30 min and sealed in a 23 mL Teflonlined autoclave. Subsequently, the resulting solution was heated to 140 °C under autogenous pressure in 30 min and kept the temperature constant for 96 h. Then the autoclave was allowed to cool naturally to room temperature. After washing with DMA several times, the yellow crystals were collected. The yield based on the rare earth nitrate: for 1: 77.5%; for 2: 52.0%; for 3: 88.9%；for 4: 49.8%; for 5: 41.8%. Elem. anal. calcd. For 1 (%): C, 32.51; H, 4.81; N, 10.53. Found: C, 32.43; H, 4.81; N, 10.52. 2 (%): C,
43.28; H, 4.81; N, 10.51. Found: C, 43.25; H, 4.80; N,10.43. 3 (%): C, 43.11; H, 4.79; N, 10.48. Found: C, 43.06; H, 4.64; N, 10.32. 4 (%): C, 43.05; H, 5.62; N, 12.30. Found: C, 43.03; H, 5.60; N, 12.27. 5 (%): C, 42.93; H, 4.77; N, 10.44. Found: C, 42.85; H, 4.68; N, 10.32. 2.2.2 Synthesis of compounds 6-7, [LnCu(IN)4∙DMA]n (Ln=Er(6), Yb(7)]. A mixture of HIN (49.2 mg，4 mmol), CuCl (39.6 mg, 0.4 mmol), Ln(NO3)3·6H2O (46.1 mg, 0.1 mmol for 6; 46.7 mg, 0.1 mmol for 7), DMA (10 mL) was stirred at room temperature for 30 min and sealed in a 23 mL Teflon-lined autoclave. Subsequently, the autoclave was heated to 140 °C under autogenous pressure in 30 min and kept the temperature constant for 96 h. Then it was allowed to cool naturally to room temperature. After washing with DMA several times, the yellow crystals were collected. The yield based on the rare earth nitrate: for 6: 78.8%; for 7: 75.7%. Elem. anal. calcd. For 6 (%): C, 41.71; H, 3.10; N, 8.69. Found: C, 41.69 ; H, 3.08; N, 8.68. 7 (%): C, 41.41; H, 3.08; N, 8.63. Found: C, 41.39 ; H, 3.08; N, 8.62. 2.3 X-ray Crystallography All data collections were carried out at 293 K on a Rigaku XtaLABmini diffractometer with MoKα monochromated radiation (λ = 0.71073 Å) using the ω–2θ scan technique. Absorption corrections were performed by the CrystalClear program. Using Olex2 [22], the structure was solved by the ShelXS structure solution program [23], and refined with the ShelXL refinement package [24] using Least Squares minimisation. All non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were riding on carbon atoms geometrically. Detailed crystallographic data and structure refinement parameters of 1-7 are summarized in Table S1. CCDC numbers for 1-7: 1853409-1853415
3 Results and discussion 3.1 Structure description 3.1.1. Crystal structures of 1-5 Single crystal X-ray diffraction analysis revealed that 1-5 crystallize in the I2/a space group, monoclinic system. Because 1-5 are isostructural, only the structure of compound 4 is described in detail. Fig. 1(a) presents a perspective view of the basic unit in 4 together with atomic labeling system. The asymmetric unit of complex 4 contains half Tb(Ⅲ) ion, one Cu (Ⅰ) ion, half Br(Ⅰ) ion, three IN anions, one protonated dimethylamine and one lattice DMA molecule. The Tb-O bond lengths are ranging from 2.276 to 2.572 Å which are comparable to those reported for the other Tb(Ⅲ) compounds [25-26]. The Tb(III) cation is coordinated with four monodentate carboxyl group oxygen atoms (O1, O3, O1A and O3A) from four IN anions and four chelated carboxyl group oxygen atoms (O5, O6, O5A and O6A) from two IN anions to form an extremely distorted {TbO8} dodecahedronal geometry. As far as the coordination geometric configuration of the Cu(Ⅰ) ion is concerned, it exhibits a tetrahedral geometry, being coordinated by one Br(Ⅰ) and three nitrogen atoms (N1B, N2B and N3) from the three IN anions. Two metal ions, Tb(III) and Cu(I), are connected through the terminal carboxylate and pyridine nitrogen
of the IN ligand end to end, forming a two-dimensional layer in the bc plane (Fig 1 (b)). The Br anion was coordinated with two Cu(I) cations from adjacent two dimensional layers (Fig. S1). As a result, the two-dimensional layers were linked via Br(Ⅰ) to form a three dimensional framework (Fig. 1(c)). Meanwhile, the protonated dimethylamines are connected with the coordinating carboxylate oxygen atoms (O2, O4) through N−H⋯O hydrogen bonding to keep the stability of the whole structure [27] (Fig. S2). Lattice DMA molecules also filled in the void of the three dimensional pillared-layer framework. Using the TOPOS 4.0 program, the Tb cations and Cu2Br units both can be regarded as 6-c nodals, the IN anions can be considered as linear. So the structure of compound 4 can be described as a pcu-type framework (Fig. 2).
Fig. 1. (a) The coordination environments of Tb(III) and Cu(I) ions of 4 drawn with the thermal ellipsoid probability of 30%. Symm. op.: A= -x, y, -0.5-z; B=x, -1+y, z; (b) View of the 2D layer; (c) View of the 3D pillared-layer structure of 4.
Fig. 2. The topology framework of 4. The purple balls represent the Tb(III) center and the green balls represent Cu2Br unit. 3.1.2. Crystal structures of 6-7 Single crystal X-ray diffraction analysis revealed that 6 crystallized in the orthorhombic system, Fdd2 space group, while 7 crystallized in the orthorhombic system, Fddd space group. However, they exhibited the same three-dimensional structures and topological structures after justifying from a careful structural analysis and the similar cell parameters presented in Table S1 of 6 and 7. The different space groups of 6 and 7 were caused by different orientations. [28] So only the structure of 7 is described in detail. The asymmetric unit contains 0.25 Yb (III) metal ion, 0.25 Cu (I) ion, one IN cation. Yb(III) was located in the center of an eight-coordinated distorted dodecahedron constructed by eight carboxyl oxygen atoms from four chelating carboxyl groups of four IN anions (Fig. 3). Yb-O bond lengths are 2.333(7) and 2.334(7)Å. Cu(I) was coordinated with four pyridine nitrogen atoms from four IN anions to assemble a perfect tetrahedral geometric configuration. The Cu-N bond length is 2.047(9)Å (Fig. 3). Actually, Yb(III) cations can be considered as tetrahedron tetrapod nodes. Each Yb(III) tetrahedron tetrapod node connected with four Cu(I) via IN anions to build up a dia framework. Two sets of dia frameworks further assemble to two-interpenetration dia framework with a channel side length of about 9.0 Å along the a axis for increasing the stability (Fig. 4). For 4-connected networks, the number of dia nets [29-30] is much bigger than those of the other well-known four-connected nbo [31] and sra [32], lvt nets [14]. Therefore, the number of interpenetrating dia frameworks is huge. To the best of our knowledge, the vast majority of interpenetrating dia are concentrated in transition metal coordination polymers, while the interpenetrating dia 3d-4f HPCs being similar to compound 7 are still very rare [34]. The channels were occupied by lattice DMA molecules. On the assumption of moving the free DMA molecules, the total potential accessible void is 2829 Å3 calculated by PLATON program [34], which is 40 % of cell total volume (7068 Å3). From the experimental conditions, the difference between compounds 1-5 and compounds 6 and 7 is the change of cuprous salt and rare earth salt, resulting in obvious structural changes. On the one hand,
the Br anion from the CuBr salt remained in the compounds 1-5, while the Cl anion from CuCl was not found in compounds 6 and 7. According to the theory of hard and soft acids and bases, the Br anion is a softer base than the Cl anion, the Cu(I) cation is a classic soft acid, therefore the Br anion was coordinated with a Cu(I) cation in compounds 1-5, while the coordinated sites of the Cu(I) cation were occupied by pyridine nitrogen atoms, which are softer than the Cl anion, in compounds 6 and 7. Thus, the secondary building units constructed by the Cu cations in compounds 1-5 were different from those in compounds 6 and 7. On the other hand, medium rare earth elements were employed in compounds 1-5, while heavy rare earth elements were used in the synthesis procedure of compounds 6 and 7. The ionic radius of medium rare earth elements is bigger than that of heavy rare earth elements due to effects of the lanthanide contraction. As a result, the secondary building units constructed by medium rare earth elements in compounds 1-5 were different from those in compounds 6 and 7. Consequentially, the structures of compounds 1-5 are completely different from the structures of compounds 6 and 7. Of course, this is exactly what we expect.
Fig. 3. The coordination environments of Yb(III) and Cu(I) cations in 7 drawn with the thermal ellipsoid probability of 30%. Symm. op.: A= 0.75-x, y, 0.75-z; B= x, 0.75-y, 0.75-z;C= 0.75-x, 0.75-y, z; D= 25-x, y, 1.25-z, E= 1.25-y, 1.25-z; F= 0.25-x, 1.25-y, z.
Fig. 4. (a) 3D two-fold interpenetrating framework of 7; (b) 3D two-fold dia interpenetrating topology of 7. 3.2. PXRD analysis, IR Spectroscopy and TGA analysis Powder X-ray diffraction (PXRD) analyses of compounds 1-7 were performed at room temperature (Fig. S3). The patterns for 1-7 were in good agreement with the simulated patterns obtained from the corresponding the single-crystal structures, confirming that the single-crystal structures are really representative for the corresponding powder samples. The FT-IR spectra of 1–7 were depicted in Fig. S4. The strong adsorption peaks in the region 1643cm-1-1542 cm-1 and 1415 cm-1-1387cm-1 are attributed to the symmetric stretching vibrations of carboxylic groups. The absence of strong bands in the range of 1690 cm-1-1730 cm-1 indicates that all carboxyl groups of HIN are deprotonated [35]. To study the thermal stability, thermogravimetric analyses of 1-7 were performed from 40 to 800 °C at a heating rate of 10 °C/min under N2 ambient. For compounds 1-5, the TGA curves are similar, compound 5 has been chosen for a detailed description. The first weight loss from 140 to 240°C corresponds to the loss of the protonated dimethylamine and lattice DMA molecules. Above 300℃, the framework gradually began to break down, the weight loss could be attributed to the decomposition of the organic ligands. For compounds 6-7, the TGA curves are roughly the same, the compound 6 is described. The first loss weight occurred about 100 to 200 ℃, corresponding to one free DMA molecule per formula, which can be confirmed via single crystal structure of the isostructural compound 7. Above 250 ℃, the structure started to decompose. The TGA results show that compounds 1-7 exhibited relatively good steady behavior. 3.3 Magnetic properties for 1, 3, 4 and 5 The magnetic susceptibility data of 1, 3, 4 and 5 were measured in the temperature range from 2 to 300 K under a 1000 Oe field, and χMT is shown in Fig. 5. For 1, the χMT value was 0.092 cm3 K mol-1 at 300 K, which was very close to the theoretical value of 0.090 cm3 K mol-1 based upon one Sm(III) ion
in the 6H5/2 ground state (g = 2/7). With decreasing temperature, the χMT value rapidly declined to a minimum of 0.035 cm3 K mol-1 at 2 K in a nearly linear relation, this maybe indicates very weak antiferromagnetic interactions between the adjacent Sm(III) ions [9]. For 3, 4 and 5, the χMT values were respectively 7.76 cm3 K mol-1, 14.26 cm3 K mol-1 and 14.03 cm3 K mol-1 at 300 K, which approaches the theoretical values of 7.88 cm3 K mol-1, 14.17 cm3 K mol-1 and 14.07 cm3 K mol-1, which were calculated based upon one Gd(III) ion in the 8S7/2 ground state (g = 2), one Tb(III) ion in the 7F6 ground state (g = 3/2), one Dy(III) ion in the 6H15/2 ground state (g = 4/3), respectively. As decreasing the temperature, the χMT values of 3, 4 and 5 decreased. Finally, the χMT value decreased to the minimum value of 6.66 cm3 K mol-1, 12.03 cm3 K mol-1 and 10.35 cm3 K mol-1 at 2K, respectively. The χMT vs. T plots of 3, 4 and 5 obey the Curie-Weiss law 1/χM = (T - θ)/C, corresponding to Curie constants C = 7.69 cm3 K mol-1, 14.26 cm3 K mol-1 and 14.30 cm3 K mol-1, and Weiss constants θ = -0.70 K, -0.65 K and -1.58 K, respectively. For 3, the trend of the χMT value and the negative value of θ indicated the existence of antiferromagnetic coupling between two Gd(III) ions [7,9]. For 4 and 5, however, the change trends of the χMT values with temperature and the negative θ value cannot unambiguously confirm antiferromagnetic coupling between two adjacent Tb(III) /Dy(III) ions because of depopulation of Stark sublevels of Tb(III) /Dy(III) can lead to decline of χMT value as lowering the temperature [7,9].
Fig. 5. Plots of χMT vs. T and χM–1 vs. T of 1, 3, 4 and 5.
4. Conclusion In summary, we have successfully synthesized seven novel 3D 3d-4f coordination polymers. Among
these compounds, 1-5 exhibited anionic three-dimensional pillared-layer frameworks with pcu topology, while 6-7 presented a rare 3d-4f two-fold interpenetrating dia-type framework. In addition, the magnetic property studies of 1, 3, 4 and 5 indicated superparamagnetic behavior.
Acknowledgements This work was supported by National Natural Science Foundation of China (21501122, 21701116 and 21671139), and the Doctoral Scientific Research Foundation of Liaoning Province (201601193). The Distinguished Professor Project of Liaoning Province (No. 2013204)
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Highlights
Two series of Ln- Cu HCPs were synthesized via tuning the CuX and lanthanum cations.
These HCPs exhibited different 3D framework.
The magnetic properties of 1, 3, 4 and 5 were investigated.
Graphical abstract