Two Series of Lanthanide Coordination Polymers with 2

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Two Series of Lanthanide Coordination Polymers with 2-Methylenesuccinate: Magnetic Refrigerant, Slow Magnetic Relaxation, and Luminescence Properties Zhong-Yi Li, Bin Zhai, Suzhi Li, Guangxiu Cao, FuQiang Zhang, Xiang-Fei Zhang, Fuli Zhang, and Chi Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00678 • Publication Date (Web): 20 Jun 2016 Downloaded from http://pubs.acs.org on June 23, 2016

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Crystal Growth & Design

Two Series of Lanthanide Coordination Polymers with 2-Methylenesuccinate: Magnetic Refrigerant, Slow Magnetic Relaxation, and Luminescence Properties Zhong-Yi Li, Bin Zhai,* Su-Zhi Li, Guang-Xiu Cao, Fu-Qiang Zhang, Xiang-Fei Zhang, Fu-Li Zhang, and Chi Zhang

College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000, P. R. China

KEYWORDS:

Lanthanide;

Coordination

Polymer;

2-Methylenesuccinate;

Magnetic

Refrigerant; photoluminescence

ABSTRACT: Two series of lanthanide coordination polymers based on 2-methylenesuccinate acid (H2MSA) ligand, {[Ln(MSA)(NO3)(H2O)2]·2H2O}n (Ln=Gd (1); Tb (2); Dy (3)) and {[Ln2(MSA)3(H2O)4]·3H2O}n (Ln=Gd (4); Tb (5); Dy (6)), have been synthesized. Compounds 1–3 exhibit a 1D zigzag chain structure, in which the neighboring Gd3+ ions are connected by two carboxylate groups from different MSA2- ligands. Compounds 4–6 all consist of unique 1D lanthanide-carboxylate building units [Ln4(CO2)6]n constructed from the adjacent Ln3+ ions and carboxyl groups of the H2MSA ligands, which can further generate 2D layer structures via the

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link of MSA2−. The magnetic study reveals that the weak ferromagnetic interactions between adjacent Gd3+ ions both exist in 1 and 4. Meanwhile, 1 and 4 display significant cryogenic magnetocaloric effects with maximum −∆Sm values of 38.86 and 39.31 J kg−1 K−1 at 2 K and 7 T, respectively, and 3 was found to exhibit slow relaxation of the magnetization. Solid state photoluminescence properties reveal that the Tb- and Dy-containing complexes 2, 3, 5 and 6 are photoluminescent materials.

INTRODUCTION In recent years, the unremitting studies for lanthanide coordination polymers have attracted great attentions in the chemistry and materials fields, because of not only their intriguing architectures and fascinating topologies, but also their potential applications such as luminescent sensing, molecular magnetism, and magnetic resonance imaging (MRI) contrast agents fields.1−5 For photoluminescence, Ln3+ cations are usually used as luminescent centers for their characteristic narrow line-like emissions in the visible to near-infrared region of the optical spectrum, due to internal 4f–4f transitions.5,6 For magnetic properties, because of the different local magnetic anisotropy and the large-spin multiplicity of the spin ground-state, Ln3+ cations have been widely used to build molecule-based magnetic materials, which could behave as single-molecule magnets (SMMs) and single-chain magnets (SCMs)7−9, especially for highly anisotropic Dy-based complexes, or as low-temperature molecular magnetic coolers for isotropic Gd-containing entities.10−13 The SMMs and SCMs display slow relaxation of the magnetization


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and could provide the promising candidates to make spintronic devices.5,6,14 While the molecular magnetic coolers, which are based on the magnetocaloric effect (MCE) and measured by the change of the magnetic entropy (∆Sm) upon application and removal of a magnetic field, are often paramagnets down to liquid helium temperatures and have potential applications as energyefficient and environmentally friendly cryogenic refrigerators.15−17 Generally speaking, an excellent molecular magnetic cooler should bear the features of a large spin ground state S, negligible magnetic anisotropy, dominant ferromagnetic interaction, and high magnetic density.18−20 Thus, multidimensional Gd-containing coordination polymers with small ligands are promising candidates because Gd3+ (S = 7/2) ion has a high isotropic spin and small organic ligands could give a large metal/ligand mass ratio to guarantee a high magnetic density.17,19 Furthermore, the metal/ligand mass ratio could also be enhanced by increasing the dimension of the structure.21,22 Since the first study of the MCE in the well-known molecule {Mn12},23 a large amount of impressive compounds associated with molecular magnetic cooling have been reported, and the largest record of –∆Sm has been breaked frequently.16,18,20 However, most of them have focused on the various discrete clusters, and the documented MCE explorations of extended Gd-containing frameworks are still limited.5,6,20−22 As one small-size flexible polycarboxylate ligand, 2-Methylenesuccinic acid (H2MSA) could display various bridging modes and has rarely been documented to construct coordination polymers.24 By investigation of H2MSA, we have obtained two series of lanthanide-based coordination polymers, one-dimensional (1D) {[Ln(MSA)(NO3)(H2O)2]·2H2O}n (Ln=Gd (1); Tb


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(2); Dy (3)) and two-dimensional (2D) {[Ln2(MSA)3(H2O)4]·3H2O}n (Ln=Gd (4); Tb (5); Dy (6)). Here, the magnetic and photoluminescent properties have been investigated. EXPERIMENTAL SECTION Materials and Physical measurements. All chemicals were obtained from commercial sources and used without further purification. Aqueous solutions of lanthanum nitrate were prepared by digesting lanthanide oxides in concentrated nitric acid. Elemental analyses were determined by a Vario EL III elemental analyzer. FT-IR spectra were recorded in the range of 4000-400 cm-1 on a JASCO FT/IR-430 spectrometer with KBr pellets. Powder X-ray diffraction (PXPD) measurements were carried out on a Bruker D8 ADVANCE X-ray Diffractometer using Cu Kα (λ = 1.5418 Å) at room temperature. Solid state luminescence properties were carried out using a F-4600 FL Spectrophotometer. Thermogravimetric analyses were performed under a flow of nitrogen (40 mL/min) at a ramp rate of 10 °C/min, using a NETZSCH STA 449F3 instrument. Magnetic measurements were performed on a Quantum Design SQUID magnetometer MPMS XL-7. The data was corrected for the sample holder and the diamagnetic contributions. Synthesis of 1–3. Compounds 1–3 were prepared under the same conditions. 0.6 mL Ln(NO3)3 (1 M, 0.6 mmol; Ln=Gd; Tb; Dy) aqueous solution, 0.026 g H2MSA (0.2 mmol) and 2 mL deionized water were placed in a 15 mL vial. 0.1 M NaOH aqueous solution was added dropwise to adjust the pH value of the resulting solution to about 5.1 under stirring. The vial was sealed


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and heated at 90°C in an oven for 24 h, then cooled to room temperature. Colourless crystals of the products were obtained. {[Gd(MSA)(NO3)(H2O)2]·2H2O}n (1): Yield, 48% based on H2MSA. Anal. Calcd. for C5H12GdNO11: C, 14.32; H, 2.88; N, 3.34%. Found: C, 14.25; H, 2.94; N, 3.28%. IR (KBr pellet, cm−1): 3518 s, 3323 s, 1652 m, 1534 s, 1448 s, 1322 s, 1228 m, 1152 w, 1025 w, 965 w, 838 m, 693 m, 592 w. {[Tb(MSA)(NO3)(H2O)2]·2H2O}n (2): Yield, 51% based on H2MSA. Anal. Calcd. for C5H12TbNO11: C, 14.26; H, 2.87; N, 3.33%. Found: C, 14.22; H, 2.91; N, 3.31%. IR (KBr pellet, cm−1): 3518 s, 3306 s, 1643 m, 1534 s, 1445 s, 1329 s, 1236 m, 1160 w, 1050 w, 965 w, 838 m, 693 m, 591 w. {[Dy(MSA)(NO3)(H2O)2]·2H2O}n (3): Yield, 46% based on H2MSA. Anal. Calcd. for C5H12DyNO11: C, 14.14; H, 2.85; N, 3.30%. Found: C, 14.18; H, 2.88; N, 3.26%. IR (KBr pellet, cm−1): 3526 s, 3314 s, 1643 m, 1533 s, 1445 s, 1329 s, 1245 m, 1151 w, 1050 w, 965 w, 838 m, 693 m, 592 w. Synthesis of 4–6. The following is the general progress for the preparation of 4–6. 0.2 mL Ln(NO3)3 (1 M, 0.2 mmol; Ln=Gd; Tb; Dy) aqueous solution, 0.078 g H2MSA (0.6 mmol) and 2 mL deionized water were placed in a 15 mL vial. 0.1 M NaOH aqueous solution was added dropwise to adjust the pH value of the resulting solution to about 4.6 under stirring. The vial was sealed and heated at 90°C in an oven for 24 h, then cooled to room temperature. Colourless crystals of the products were obtained.


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{[Gd2(MSA)3(H2O)4]·3H2O}n (4): Yield, 58% based on Gd3+. Anal. Calcd. for C15H26Gd2O19: C, 21.84; H, 3.18%. Found: C, 21.68; H, 3.22%. IR (KBr pellet, cm−1): 3348 s, 1652 m, 1550 s, 1440 s, 1245 m, 1169 w, 949 m, 838 m, 659 w, 549 w. {[Tb2(MSA)3(H2O)4]·3H2O}n (5): Yield, 56% based on Tb3+. Anal. Calcd. for C15H26Tb2O19: C, 21.75; H, 3.16%. Found: C, 21.62; H, 3.14%. IR (KBr pellet, cm−1): 3247 s, 1660 m, 1550 s, 1440 s, 1245 m, 1177 w, 949 m, 838 m, 668 w, 549 w. {[Dy2(MSA)3(H2O)4]·3H2O}n (6): Yield, 52% based on Dy3+. Anal. Calcd. for C15H26Dy2O19: C, 21.57; H, 3.14%. Found: C, 21.45; H, 3.15%. IR (KBr pellet, cm−1): 3348 s, 1652 m, 1550 s, 1440 s, 1245 m, 1177 w, 948 m, 838 m, 668 w, 549 w. X-ray Crystallography. Crystallographic data of complexes 1−6 were collected on a Bruker D8 Quest CMOS area detector system with graphite-monochromated Mo-Kα (λ = 0.71073 Ǻ) radiation. Data reduction and unit cell refinement were performed with Smart-CCD software25. The structures were solved by direct methods and refined by full-matrix least squares methods using SHELXL-97.26 For 1−6, All non-hydrogen atoms were refined anisotropically. Hydrogen atoms on organic ligands were placed in idealised positions and refined using a riding model. Hydrogen atoms on the terminal and free water molecules were initially found on Fourier difference maps and then restrained by using the DFIX instruction. Exceptionally, no attempts were made to locate the hydrogen atoms on the free water molecule O19 in 4−6. A summary of the important crystal and structure


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refinement data of 1−6 was given in Table 1. Selected bond lengths and angles for 1 and 4 were listed in Table S1 and S2, respectively. Table 1. Crystal data and structure refinement of 1–6. 1

2

3

4

5

6

Formula

C5H12GdNO11

C5H12TbNO11

C5H12DyNO11

C15H26Gd2O19

C15H26Tb2O19

C15H26Dy2O19

Mr.

419.41

421.08

424.66

824.86

828.20

835.36

T (K)

298(2)

298(2)

298(2)

298(2)

299(2)

298(2)

Cryst. system

Monoclinic

Monoclinic

Monoclinic

Triclinic

Triclinic

Triclinic

Space group

C2/c

C2/c

C2/c

P-1

P-1

P-1

a /Å

22.4276(18)

22.3816(9)

22.3394(10)

10.8212(9)

10.7889(13)

10.7695(8)

b /Å

8.2675(7)

8.2600(4)

8.2424(4)

10.8929(9)

10.8561(14)

10.8402(7)

c /Å

15.7031(12)

15.6792(7)

15.6597(8)

11.9677(10)

11.9524(15)

11.9622(8)

α/°

90

90

90

103.161(2)

103.267(6)

103.486(2)

β/°

125.077(2)

125.0730(10)

125.077(2)

112.858(2)

112.925(5)

112.992(2)

γ/°

90

90

90

101.710(2)

101.538(6)

101.352(3)

V (Å3)

2382.9(3)

2372.31(18)

2361.8(2)

1197.15(17)

1187.7(3)

1183.69(14)

Z

8

8

8

2

2

2

dcalcd., g/cm3

2.338

2.358

2.388

2.288

2.316

2.344

µ(mm-1)

5.621

6.017

6.382

5.581

5.996

6.354

F(000)

1608

1616

1624

792

796

800

Reflections collected/ unique

15131 / 2060

15685 / 2058

15249 / 2030

38074 / 4187

31269 / 4173

17719 / 4152

R(int)

0.0406

0.0397

0.0310

0.0239

0.0483

0.0395

GOF on F2

1.045

1.059

1.053

1.060

1.067

1.066

R1a(I > 2σ (I))

0.0224

0.0193

0.0183

0.0203

0.0295

0.0308

wR2b(all data )

0.0578

0.0499

0.0470

0.0543

0.0817

0.0767

a

R1= ∑(||Fo|-|Fc||) / ∑ |Fo| , bwR2 = {∑w [(F2o − F2c)] / ∑w [(F 2o )2]}0.5


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RESULTS AND DISCUSSION Synthesis. The one-dimensional {[Ln(MSA)(NO3)(H2O)2]·2H2O}n (Ln=Gd (1); Tb (2); Dy (3)) and two-dimensional {[Ln2(MSA)3(H2O)4]·3H2O}n (Ln=Gd (4); Tb (5); Dy (6)) lanthanide coordination polymers have been synthesized hydrothermally based on H2MSA ligand. H2MSA and Ln(NO3)3 with a molar ratio of 1:3 could lead to the 1D structures, while 3:1 molar ratio gave the 2D architectures. Given that the similar pH values (5.1 for 1-3 and 4.6 for 4-6), the molar ratio of H2MSA and Ln(NO3)3 may play an important role for the formation of the two systems. Full synthetic details are given in the Experimental Section. Crystal Structures of 1−3. Single crystal X-ray diffraction analyses reveal that compounds 1−3 are isostructural and only the structure of 1 will be discussed in detail. 1 crystallizes in the monoclinic C2/c space group and has a 1D zigzag chain structure. As shown in Figure 1a, the asymmetric unit of 1 consists of one Gd3+ ion, one MSA2- ligand, one nitrate anion, two coordinated and two lattice water molecules. The Gd3+ ion is nine-coordinated and bears a distorted square antiprismatic geometry, which is completed by five oxygen atoms (O1, O3, O1A, O2A and O4B) from three MSA2- ligands, two oxygen atoms (O5 and O6) from one nitrate anion, and two oxygen atoms (O8w and O9w) from coordinated water molecules. The Gd−O bond lengths and O−Gd−O bond angles are in the range of 2.303(3)−2.745(4) Å and 48.14(10)−157.63(11)°, respectively, which are in agreement with those in the reported Gdcontaining compounds.20−21


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(a)

(b)

(c)

Figure 1. (a) Coordination environment of the Gd3+ ion in compound 1. Symmetry codes: A, 0.5-x, -0.5+y, 0.5-z; B, 0.5-x, 0.5+y, 0.5-z. (b) View of the 1D chain structure of 1. (c) Packing View of the 1D chains viewed along [110] axis. The free water molecules are shown in spacefilling mode, and the hydrogen atoms have been omitted for clarity. Each of the MSA2- ligands in 1 uses one tridentate bridging carboxylic group and one bidentate bridging carboxylic group to connect three Gd3+ ions (mode I in Scheme 1). The coordination mode could be described as µ3-η1: η2: η1: η1. Around every Gd3+ ion, there are three MSA2ligands, by which the Gd3+ ions connect each other to produce a 1D zigzag chain (Figure 1b). It is noted that all the neighboring Gd3+ ions are linked together by one tridentate and one bidentate carboxylate groups from different MSA2- ligands (Figure S2). The Gd···Gd distance is 4.69(1) Å, and the Gd−Gd−Gd angle is 123.78(1)°. Figure 1d shows the packing view of the structures


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viewed along [110] axis, and free water molecules are filled between the adjacent chains, which are structurally well isolated due to the absence of significant interchain hydrogen bonding interactions.

I

II

III

IV

Scheme 1. Coordinate modes of MSA2- ligands in compounds 1 (I) and 4 (II-IV).

Crystal Structures of 4−6. Compounds 4−6 are also isostructural. 4 crystallizes in the triclinic P-1 space group and has a 2D layer structure. As shown in Figure 2a, the asymmetric unit of 4 contains two Gd3+ ions, three MSA2- ligands, four coordinated and three lattice water molecules. The two Gd3+ ions bear two different coordination environments. The coordination geometry of the nonacoordinate Gd1 ion can be described as a monocapped square antiprism, featuring coordination by eight oxygen atoms (O4, O6, O3A, O4A, O8B, O9B, O12C and O13C) from four MSA2- ligands, and one oxygen atom (O5w) from terminal water molecule. In contrast, Gd2


10

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ion is eight-coordinated and has a {O8} square antiprismatic donor set, formed by five oxygen atoms (O7, O10, O1D, O2D and O11E) from three MSA2- ligands and three oxygen atoms (O14w, O15w and O16w) from three terminal water molecules. The bond lengths of Gd−O and the angles of O−Gd−O fall in the range of 2.313(3)−2.715(3) Å and 49.87(9)−158.87(12)°, respectively, which are similar to those in 1. (a)

(b) (c)

Figure 2. (a) Coordination environment of two asymmetric Gd3+ ions in compound 4. Symmetry codes: A, 1-x, -y, 1-z; B, 1-x, 1-y, 1-z; C, -x, -y, -z; D, -1+x, y, -1+z; E, -x, 1-y, -z. (b) The 1D chain-shaped building units [Gd4(CO2)6]n constructed from the adjacent Gd3+ ions and carboxyl groups of the H2MSA ligands in 4. (c) View of the 2D layer structure of 4. The hydrogen atoms have been omitted for clarity.


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In the structure, the MSA2- ligands present three types of coordination modes (II−IV), µ3-η2: η1: η1: η1, µ3-η1: η1: η1: η1 and µ3-η1: η1: η1: η1 (Scheme 1). For mode II, the MSA2- ligand bears one tridentate and one chelating bidentate bridging carboxylic group. For modes III and IV, the MSA2- ligands both have one bidentate and one chelating bidentate bridging carboxylic group. However, the bidentate carboxylate groups display different Gd-O-C angles, 114.068(5) and 171.660(11)° for mode III, and 146.568(7) and 153.578(6)° for mode IV. Interestingly, two symmetry-related Gd1 ions are connected through two tridentate carboxylate groups (mode II), while two symmetry-related Gd2 ions are linked by two bidentate carboxylate groups (mode III). The Gd1 ion pair and Gd2 ion pair futher connect each other by bidentate carboxylate groups (mode IV) to form the 1D [Gd4(CO2)6]n chain (Figure 2b). The adjacent chains are joined together by the chelating bidentate carboxylate groups of the MSA2- ligands with modes II-IV to form the 2D layer strusture (Figure 2c and Figure S4). Between the layers, free water molecules are filled (Figure S5). The Gd1···Gd1, Gd2···Gd2 and Gd1···Gd2 distances are 4.28(1), 4.53(1) and 5.77(1) Å, respectively. These are different from the identical Gd···Gd distance of 4.69(1) Å in 1, indicating that the two systems would display different magnetic properties. Thermal Analysis and PXRD Patterns. The thermal stabilities of 1−6 were studied on the crystalline samples under the N2 atmosphere from 25 to 800 °C (Figure S8). The thermogravimetric (TG) curves show that six polymers undergo two kinds of weight loss processes because of the isomorphic feature of 1−3 and 4−6, respectively. The weight losses of


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1−3 in the range of 25−165 °C are 16.70%, 17.19% and 17.52%, respectively, corresponding to the release of the coordinated and free water molecules (calcd.: 17.18% for 1, 17.11% for 2 and 16.97% for 3). Above 165 °C, the weight losses may be attributed to the decomposition of the anhydrous compositions. For 4−6, the TG curves are very similar and two mass loss steps are observed. The first weight losses of 4−6 in the range of 25–380 °C are 14.92%, 15.36% and 15.55%, respectively, which are ascribed to the release of four coordinated and three free water molecules for per formula unit. After 380 °C, the weight losses are due to the collapse of the framework. The PXRD experimental and computer-simulated patterns of compounds 1−6 are shown in Figure S9 and S10. The PXRD patterns of the bulk samples are in good agreement with their simulated patterns from the single-crystal structures, demonstrating the phase purity. Magnetic Properties. The magnetic susceptibilities of 1−6 have been researched in the temperature range of 1.8−300 K with an applied direct current (dc) magnetic field of 1000 Oe, as shown in Figure 3. At room temperature, the χMT values of 1 and 4 are 7.51 and 16.18 cm3 mol-1 K, which are close to the expected values of 7.88 cm3 mol-1 K (calculated for one Gd3+ (S =7/2, g = 2) ion) and 15.76 cm3 mol-1 K (calculated for two isolated Gd3+ (S =7/2, g = 2) ions), respectively. Upon cooling, the χMT values of 1 and 4 decrease gradually to a minimum of 7.18 cm3 mol-1 K at 35 K and 15.92 cm3 mol-1 K at 23 K, respectively, and then increase quickly to 7.68 cm3 mol-1 K and 16.70 cm3 mol-1 K at 1.8 K. The increases of χMT values in lowtemperature region indicate the existence of possible weak ferromagnetic interactions between adjacent Gd3+ ions.


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Figure 3. Temperature dependence of the χMT values for 1-6 at 1000 Oe dc magnetic field. The solid line represents the best fit to the data of 1 and 4 with the parameters in the text. Given the strictly 1D chain structure of 1, the expression deduced by Fisher27 (eq 1) could be used to quantitatively analyze the interaction between adjacent Gd3+ ions with a large spin value of S = 7/2.5,28

Ng 2b 2 1 + u c chain = S ( S + 1) 3kT 1- u

(1)

where, u = cth(JS(S + 1)/kT) - kT/JS(S + 1) In the equation, N is Avogadro’s number, β is the Bohr magnetron, k is the Boltzmann constant, and J is the exchange coupling parameter between adjacent spins. The best fitting of the susceptibility data for 1 yields g = 1.93(1), J = 0.0023(1) cm−1 and R = 2.26 × 10−4, where R is calculated from Σ[(χMT)obsd −(χMT)calcd]2 / Σ[(χMT)obsd]2. The positive and small J value is in good agreement with the reported values for other carboxyl-bridged Gd-containing complexes,5,21,28


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suggesting that very weak ferromagnetic coupling exists between adjacent Gd3+ ions in the 1D chain. As described in the crystal structure part, adjacent Gd3+ ions are bridged by carboxylate groups to give a [Gd4(CO2)6]n chain in 4, and Gd1···Gd1, Gd2···Gd2 and Gd1···Gd2 distances are 4.28(1), 4.53(1) and 5.77(1) Å, shorter than the distance between adjacent 1D chains connected by MSA2- ligands (longer than 6.5 Å). For convenience of data analysis, the magnetic exchange interaction through the MSA2- bridge was considered to be negligible and the exchange interactions of Gd1···Gd1 and Gd2···Gd2 be same. Therefore, the 1D chain can be treated as alternating uniform Gd2 dimers with the different intradimeric and intrachain exchange constant (Jd vs Jc).29

cd =

2 Ng 2 b 2 ´ (140e56 J / kT + 91e 42 J / kT + 55e30 J / kT kT + 30e 20 J / kT + 14e12 J / kT + 5e6 J / kT + e2 J / kT ) /(15e56 J / kT + 13e42 J / kT + 11e30 J / kT + 9e20 J / kT + 7e12 J / kT + 5e6 J / kT + 3e2 J / kT + 1)

cd =

Ng 2b 2 Sd ( Sd + 1) 3kT

(2)

(3)

Ng 2 b 2 1 + u c chain = Sd ( Sd + 1) 3kT 1- u

(4)

where, u = cth(JcSd(Sd + 1)/kT) - kT/JcSd(Sd + 1) Using this rough model, the best fitting of the susceptibility data for 4 gives g = 2.02(1), Jd = 0.0055(1) cm−1, Jc = 0.14(1) cm−1 and R = 3.58 × 10−5. The positive and small parameters show


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Page 16 of 30

that intradimeric Gd1···Gd1, Gd2···Gd2 and intrachain Gd1···Gd2 interactions in 4 all are weakly ferromagnetic, which are comparable to that in 1.

(a)

(b)

(c)

(d)

Figure 4. Field dependence of the magnetization plots of 1 (a) and 4 (b) at the indicated temperatures. −∆Sm calculated from the magnetization data of 1 (c) and 4 (d) at various fields and temperatures.

The magnetization data of 1 and 4 are collected at a field of 0−7 T between 2 and 7 K (Figure 4a and 4b). The M versus H curves show a steady increase with the increasing field and saturation values of 7.01 Nβ for 1 and 13.97 Nβ for 4 at 7 T and 2 K, which are extremely approximate with the expected value of 7 and 14 Nβ for one and two spin-only Gd3+ (S = 7/2, g


16

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= 2) ions, respectively. To evaluate the MCE, the magnetic entropy changes ∆Sm of 1 and 4 could be calculated from the M versus H data by using the Maxwell equation:5,30 D S m (T ) =

ò [¶ M (T , H ) / ¶ T ]

dH

H

(5)

According to eq 5, the −∆Sm values of 1 and 4 can be obtained, as shown in Figure 4c and 4d. For 1, the maximum value of −∆Sm is 38.86 J K−1 kg−1 for a field change ∆H = 7 T at 2.0 K, which is relatively large value among molecular magnetic coolants,18 and comparable with those for the reported impressive Gd-based polymers,13,20,21 such as 45.0 J kg−1 K−1 at 1.8 K and ∆H = 7 T for the 1D chain [Gd(OAc)3(MeOH)]n21 and 42.8 J kg−1 K−1 at 2.6 K and ∆H = 7 T for the 3D framework [Gd2(OH)2(suc)2(H2O)]n·2nH2O.13 Theoretically, the full entropy change per mole of compound corresponding to one Gd3+ ion is 41.22 J K−1 kg−1, as calculated from the equation R ln(2S+ 1), where S = 7/2. The difference of −∆Sm between the theoretical and experimental values may be due to the MW/NGd ratio of 419 (where MW is the molecular mass of 419.41 g mol−1 and NGd is the number of Gd3+ ion present per mole of 1) and the interchain antiferromagnetic interaction in 1.22,30 For 4, the maximum value of −∆Sm is 39.31 J K−1 kg−1 (calculated from 2Rln(2S + 1), expected maximum −∆Sm is 41.92 J K−1 kg−1) at 2.0 K and ∆H = 7 T, slightly larger than that of 1. Considering the similar weak ferromagnetic coupling between the Gd ions in 1 and 4, the major cause could be ascribed to the smaller MW/NGd ratio (412) in

4.20,21 Generally, a lower MW/NGd ratio meaning a higher Gd(III) density, may result in a larger MCE.21


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Page 18 of 30

For 2, 3, 5 and 6, the χMT values at 300 K are 11.98, 14.40, 23.80 and 28.67 cm3 mol-1 K, respectively, which are in agreement with the expected values, 11.81 cm3 mol-1 K for 2 ( one Tb3+ (S = 3, L = 3, g = 3/2) ion), 14.18 cm3 mol-1 K for 3 (one Dy3+ (S = 5/2, L = 5, g = 4/3) ion), 23.62 cm3 mol-1 K for 5 (two uncoupled Tb3+ (S = 3, L = 3, g = 3/2) ions) and 28.36 cm3 mol-1 K for 6 (two isolated Dy3+ (S = 5/2, L = 5, g = 4/3) ions). With lowering the temperature, the χMT values of 2 and 5 decrease gradually to 10.07 cm3 mol-1 K around 9 K and 20.96 cm3 mol-1 K around 30 K and then decrease abruptly to 7.84 cm3 mol-1 K and 14.11 cm3 mol-1 K at 1.8 K, respectively. The χMT values of 6 decrease gradually to 21.70 cm3 mol-1 K at 1.8 K, while the χMT values of 3 decrease gradually to a minimum of 13.25 cm3 mol-1 K at 4.5 K before increasing gradually to 13.43 cm3 mol-1 K at 1.8 K. The decrease of χMT values may be ascribed to a combination of the antiferromagnetic interactions between the metal centers, the progressively thermal depopulation of the ground-state Ln3+ sublevels as well as the magnetic anisotropy, which is hard to clearly distinguish each contribution.10,31 While the increase of χMT values below 4.5 K for 3 suggests the presence of the ferromagnetic interactions between the adjacent Dy3+ ions within the 1D chain.32 The field-dependent magnetization of 3 measured at 2.0 K (Figure S11) displays a rapid increase under low fields and then slowly reaches the maximum of 5.05 Nβ at 7 T. The maximum value is significantly smaller than the theoretical saturation values (10 Nβ) for one magnetically

isolated

Dy3+

ion.

The

unsaturated

magnetization

together

with

the


18

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nonsuperimposed M versus H/T curves (Figure S12) suggest the existence of significant magnetoanisotropy and/or low-lying excited states.6,10,19

(a)

(b)

Figure 5. (a) Temperature dependence of the out-of-phase (χ″) ac susceptibility for 3 at the indicated frequencies and in the zero dc field. (b) Plot of ln(χ″/χ′) versus 1/T for 3. The red solid lines represent the fitting results over the range of 100−970 Hz.


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To investigate the magnetization dynamics, alternating current (ac) susceptibility measurements for 2, 3, 5 and 6 were carried out at zero direct-current (dc) fields. For 2, 5 and 6, no out-of-phase signal is observed. In contrast, as shown in Figure 5a, obvious frequencydependent out-of-phase signals (χ″) were observed for 3 below about 7 K, indicating the presence of slow magnetic relaxation. Unfortunately, no peak of χ″ is observed, which is usually encountered in Dy3+ complexes.5,7 Thus, the energy barrier of 3 could not be obtained by Arrhenius fitting. Assuming that only one relaxation process exists in 3, the energy barrier (Ea) and τ0 values could be evaluated roughly from fits of the ac susceptibility data by adopting the Debye model and using the relationship ln(χ″/χ′)=ln(ωτ0)+Ea/kBT,33 giving Ea ≈ 1.88 K and τ0 ≈ 0.24 × 10−6 s (Figure 5b), which are comparable with the expected numbers (τ0 = 10−6−10−11 s) for SMMs.5,7,34

Luminescent properties. The luminescence spectra of complexes 2, 3, 5 and 6 were investigated in the solid state at room temperature because of the existence of Tb3+ and Dy3+ ions. As shown in Figure 6, the excitation spectra of 2 and 3 are similar to 5 and 6, respectively. Upon excitation at 354 nm, complexes 2 and 5 exhibit green luminescence with characteristic Tb3+ bands at ca 491, 547, 586, and 623 nm, which are attributed to the 5D4→7FJ (J = 6, 5, 4, 3) transitions of Tb3+ centers.19 The most intense emission is centered at 547 nm and corresponds to the hypersensitive transition 5D4→7F5, which is consistent with the Tb3+ compounds reported previously.6,35 When excited at 350 nm, compounds 3 and 6 display two relatively weak emissions at 482 and 574 nm, which correspond to the characteristic emission of 4F9/2 → 6HJ (J =


20

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15/2 and 13/2) transitions of Dy3+ ions.4 The characteristic blue emission of the 4F9/2 → 6H15/2 transition is stronger than the yellow emission of 4F9/2→6H13/2, so that the Dy3+ compound emits blue light.4,36

Figure 6. The solid-state photoluminescence spectrums of 2, 3, 5 and 6 at room temperature.

CONCLUSION In summary, two families of lanthanide-based coordination polymers with 1D chain (1–3) or 2D layer structures (4–6) have been successfully synthesized by controlling the using amount of H2MSA and Ln(NO3)3. Magnetic studies show that the Dy-based compound 3 displays slow relaxation of the magnetization, and the Gd-containing complexes 1 and 4 both are weak ferromagnetic coupling between the metal centers and exhibit significant cryogenic MCEs, with the maximum −∆Sm values of 38.86 and 39.31 J kg−1 K−1 at 2 K and 7 T, respectively. Additionally, the Tb- and Dy-containing complexes 2, 3, 5 and 6 display the characteristic lanthanum luminescence at room temperature.


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ASSOCIATED CONTENT

Supporting Information. Crystal data, additional crystallographic diagrams and magnetic diagrams, IR spectra, TG curves and PXRD patterns. This material is available free of charge via the Internet at http://pubs.acs.org. Crystallographic data for 1−6 have been assigned the CCDC numbers 1477387−1477392 by the Cambridge Crystallographic Data Centre.

AUTHOR INFORMATION

Corresponding Author *E-mail: [email protected]

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT

This work was supported by the National Natural Science Foundation of China (NSFC) (grant numbers 21401126, 21571123, 21471095, 21371114, 21271125 and 21501117), Scientific and Technological Projects of Science and Technology Department of Henan province (122102210255, 152102310353).

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Two Series of Lanthanide Coordination Polymers with 2Methylenesuccinate: Magnetic Refrigerant, Slow Magnetic Relaxation, and Luminescence Properties

Zhong-Yi Li, Bin Zhai,* Su-Zhi Li, Guang-Xiu Cao, Fu-Qiang Zhang, Xiang-Fei Zhang, Fu-Li Zhang, and Chi Zhang

Three 1D chain (1–3) and three 2D layer (4–6) lanthanide coordination polymers have been successfully synthesized by controlling the using amount of H2MSA and Ln(NO3)3. The Dybased 3 shows slow relaxation of the magnetization, and the Gd-based 1 and 4 both display weak ferromagnetic coupling interaction and significant cryogenic MCEs. Furthermore, the Tb- and Dy-containing complexes display the characteristic lanthanum luminescence.


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Two Series of Lanthanide Coordination Polymers with 2

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