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Two types of Cu-Ln Heterometallic Coordination Polymers with 2Hydroxyisophthalate: Syntheses, Structures and Magnetic Properties Kai Wang, Zilu Chen, Huahong Zou, Zhong Zhang, Wei-Yin Sun, and Fupei Liang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b00327 • Publication Date (Web): 22 Apr 2015 Downloaded from http://pubs.acs.org on May 3, 2015

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Crystal Growth & Design

Two types of Cu-Ln Heterometallic Coordination Polymers with 2-Hydroxyisophthalate: Syntheses, Structures and Magnetic Properties Kai Wang,†,‡ Zi-Lu Chen,‡ Hua-Hong Zou,‡ Zhong Zhang,‡ Wei-Yin Sun,† Fu-Pei Liang∗,‡,§

†

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing, 210093, China

‡

State Key Laboratory Cultivation Base for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmacy, Guangxi Normal University, Guilin, 541004, China §

Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional

Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, 541004, China E-mail address: [email protected] (F. Liang)

1

ACS Paragon Plus Environment


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ABSTRACT: Two types of Cu-Ln heterometallic coordination polymers (CPs), [Ln4Cu8(ipO)8(ox)2(H2O)12] (Ln = Sm (1); Eu (2); ipO = 2-hydroxyisophthalate; ox = oxalate) (type I) and [Ln2Cu6(ipO)6(H2O)12] [Ln = Gd (3); Tb (4); Dy (5)] (type II) were synthesized under the same hydrothermal conditions and structurally characterized. The first type of CPs displays a 3D framework with a rare case of MoGe2 topology based on {Cu8} and {Ln2} Second Building Units (SBUs), while the second type of CPs exhibits a chain structure built up from {Cu6} SBUs and Ln ions. Both of the {Cu8} and {Cu6} SBUs consist of planar [Cu2(ipO)2]2− units linked together by weak Cu-O bonds and π-π interactions. The structural variation from type I to type II can be ascribed to different reactions of H3ipO ligands induced by lanthanide ions. The magnetic investigations revealed that 3 displays a magnetocaloric effect (MCE) with the maximum −∆Sm value of 13.97 J kg-1 K-1 for ∆H = 50 kOe at 4.0 K. It was also found that 5 displays field induced single molecular magnet (SMM) behaviors of slow magnetic relaxation and magnetization hysteresis, with an energy barrier Ueff = 63.68 K and pre-exponential τ0 = 3.77 × 10−8 s.

INTRODUCTION Due to the intriguing architectures and fascinating topologies, as well as the novel properties and potential applications in the fields of physics, chemistry, and materials science, 3d-4f CPs have attracted increasingly interests in recent years.1,2 Particularly, the promising applications as molecular magnetic materials have drawn much attentions of researchers on the magnetic properties of 3d-4f CPs.3,4 With the favorable combination of high ground state spin (S) and magnetic anisotropy (D) of 2


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the metal ions, some members of this family have been found to show anisotropic energy barriers (Ueff) that prevent the reversal of the molecular magnetization, leading to SMM or Single Chain Magnet (SCM) behaviors such as slow magnetic relaxation and magnetization hysteresis.5,6 When the lanthanide ion is Gd(III) ion with negligible magnetic anisotropy and large spin ground state, large MCE seems to be possible in the resultant CPs. The MCE is a crucial property for magnetic refrigeration, which has been proposed as possible alternative technology for ultra-cold and cryogenic sensors in aerospace devices.7-9 Among the magnetic properties of various 3d-4f CPs, those of Cu-Ln CPs have been well studied since the ferromagnetic interactions of a Cu-Gd system were observed.10-16 However, only limited examples of Cu-Ln CPs were found to show SMM/SCM behaviors17-20 or MCE21,22 until now. On the other hand, a number of discrete Cu-Ln clusters with desirable magnetic properties have been successfully obtained,23-27 and in particular that Cu-Dy pair has been proved to be an useful building block for high-performance SMMs.26,27 This implies that the study of the synthesis and magnetic properties of Cu-Ln CPs remains still an interested subject. Due to the different coordination preference of Ln(III) and Cu(II) ions to O- and N-donors,28,29 the most of previously reported Ln-Cu CPs were synthesized with ligands containing both N- and O-donors, such as carboxylate ligands with N-donors,11-16,19-22,30 salicylic Schiff bases,31,32 acetylacetonate ligand with N-donors.33 Those built by the ligands with only O-donors are relatively rare.17,34,35 On the basis of our previous study,36,37 we noted that 2-hydroxyisophthalic acid (H3ipO), a ligand with exclusive O-donors, might be a good candidate for constructing Cu-Ln CPs. The two coordinating pockets between phenolic and carboxylic oxygen atoms in this 3



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ligand would prefer chelating with Cu(II) ions to Ln(III) ions of large radii. Furthermore, the weak interactions (weak Cu-O bonds and π-π interactions), which were found frequently in Cu-H3ipO CPs,38,39 might act as a structural directing factor for building fascinating Cu-Ln CPs. With this consideration in mind, we decided to explore the possibility of synthesizing novel Cu-Ln CPs using H3ipO as ligand, and we isolated two types of compounds, [Ln4Cu8(ipO)8(ox)2(H2O)12] (Ln = Sm (1); Eu (2)] (type I) and [Ln2Cu6(ipO)6(H2O)12] [Ln = Gd (3); Tb (4); Dy (5)] (type II). The investigations show that the structures of the CPs display a variation from 3D framework with a rare MoGe2 topology based on {Cu8} SBUs and {Ln2} SBUs for type I to chain structure based on {Cu6} SBUs and mononuclear Ln(III) ions for type II. Magnetic measurements indicate that 3 shows MCE and 5 shows typical field induced SMM behaviors.

EXPERIMENTAL SECTION General Materials and Methods All reagents were used as received without further purification. 2-hydroxyisophthalic acid (H3ipO) was prepared according to reference.36 IR spectra were recorded in the range of 4000-400 cm−1 on a Perkin-Elmer Spectrum One FT/IR spectrometer using a KBr pellet. Elemental analyses for C and H were carried out on a Model 2400 II, Perkin-Elmer elemental analyzer. The powder X-ray diffraction (PXRD) data were collected with a Rigaku D/max 2500v/pc diffractometer with Cu-Kα radiation (λ = 1.5418 Å). The thermal analyses were performed on a Pyris Diamond TG/DTA with a heating rate of 10 °C min−1 in N2 atmosphere. Magnetic susceptibility measurements 4


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were performed in the temperature range of 300-2 K using a Quantum Design MPMS SQUIDXL-5 magnetometer equipped with a 5 T magnetic fields. The diamagnetic corrections for these complexes were estimated using Pascal’s constants, and magnetic data were corrected for diamagnetic contributions of the sample holder. X-ray Structure Determination All the data for CPs 1-5 were collected with a Bruker SMART CCD instrument by using graphite monochromatic Mo-Kα radiation (λ = 0.71073 Å) at 296.15 K (150.00 K for 2). Absorption effects were corrected by semi-empirical methods. The structures were solved by direct methods and were refined by full-matrix least-squares methods with the SHELXL-97 crystallographic software package and Olex2.40,41 The non-hydrogen atoms were refined anisotropically. The hydrogen atoms were placed in calculated positions and refined by using a riding model. The final cycle of full-matrix least-squares refinement was based on observed reflections and variable parameters. A summary of crystal data and relevant refinement parameters for 1-5 are given in Table 1. Selected bond lengths and bond angles are given in Table S2-S6 in the Electronic Supplementary Information (ESI). The CCDC numbers of 1, 2, 3, 4 and 5 are 1038490, 1038488, 1038489, 1038491 and 1038487, respectively. Syntheses of 1-5 A mixture of Ln(NO3)2·6H2O (0.05 mmol, Ln = Sm, Eu, Gd, Tb, Dy), Cu(OAc)2·H2O (0.05 mmol) and H3ipO (0.10 mmol) in 10 mL H2O was sealed in a Teflon-lined stainless autoclave after stirring for several minutes. The autoclave was heated to 140 °

C for 72 h followed by cooling to room temperature at a rate of 0.5 °C min−1. Green

block-shaped crystals obtained were washed with water and dried in the air. 5



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Table 1. Crystal data and structure refinement parameters for 1-5 Identification

1

4

5

Formula

C34H24Cu4Sm2O30 C34H24Cu4Eu2O30 C24H21Cu3GdO21

C24H21Cu3TbO21

C24H21Cu3DyO21

Fw

1467.39

1470.61

993.28

994.98

998.53

Temp/K

296.15

150.00

296.15

296.15

296.15

2

3

Crystal system

triclinic

triclinic

triclinic

triclinic

triclinic

Space group a/Å

P1 11.5654(2)

P1 11.5374(4)

P1 9.8540(8)

P1 9.87924(2)

P1 9.8558(5)

b/Å

13.0337(2)

12.9882(4)

12.1938(8)

12.1357(3)

12.1424(6)

c/Å

14.192(2)

14.0916(5)

12.7115(8)

12.7211(3)

12.7113(6)

α/°

63.048(2)

62.648(4)

116.079(6)

116.174(2)

116.010(5)

β/°

83.259(3)

83.193(3)

96.789(6)

96.5555(2)

96.509(4)

γ/°

80.009(2)

80.362(3)

92.058(6)

92.0057(2)

92.511(4)

V/Å3

1876.2(4)

1847.00(1)

1355.64(2)

1353.57(6)

1350.84(1)

Z

2

2

2

2

2

Dc/g cm–3

2.597

2.644

2.433

2.441

2.455

µ/mm

5.426

5.728

4.841

5.011

5.169 972

–1

F(000)

1416

1420

968

970

Reflns collected

39105

17405

15117

25089

12322

Unique reflns

8593

6501

6152

4757

4743

Rint

0.0370

0.0344

0.0693

0.0362

0.0425

GOF

1.119

1.049

1.009

1.108

1.001

R1 = 0.0292,

R1 = 0.0345,

R1 = 0.0508,

R1 = 0.0433,

R1 = 0.0334,

wR2 = 0.0836

wR2 = 0.0695

wR2 = 0.0652

wR2 = 0.1251

wR2 = 0.0678

R1 = 0.0407,

R1 = 0.0488,

R1 = 0.0800,

R1 = 0.0474,

R1 = 0.0448,

wR2 = 0.1005

wR2 = 0.0736

wR2 = 0.0766

wR2 = 0.1276

wR2 = 0.0709

R1, wR2 (I > 2σ(I)) R1, wR2 (all data)

[Sm4Cu8(ipO)8(ox)2(H2O)12] (1). Yield: 18% (based on Cu2+). Elemental analysis (%) calcd.: C, 27.83; H, 1.65. Found: C, 27.66; H, 1.79. IR (KBr disk, cm-1) selected bands: 3446 (w), 1594 (m), 1540 (w), 1446 (s), 1374 (s), 1287 (w), 1097 (w), 944 (w), 841 (w), 754 (s), 631 (w), 513 (w). [Eu4Cu8(ipO)8(ox)2(H2O)12] (2). Yield: 21% (based on Cu2+). Elemental analysis (%) calcd.: C, 27.77; H, 1.64. Found: C, 27.83; H, 1.52. IR (KBr disk, cm-1) selected bands: 3487 (w), 1594 (m), 1537 (w), 1440 (s), 1378 (m), 1286 (w), 1078 (m), 945 (w), 875 (w), 757 (m), 631 (w), 539 (w). [Gd2Cu6(ipO)6(H2O)12] (3). Yield: 31% (based on Cu2+). Elemental analysis (%) calcd.: C, 29.02; H, 2.13. Found: C, 29.11; H, 2.25. IR (KBr disk, cm-1) selected 6


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bands: 3399 (w), 1596 (m), 1544 (m), 1442 (vs), 1370 (s), 1285 (m), 1158 (w), 1100 (w), 940 (m) , 840 (m) , 754 (vs) , 634 (m). [Tb2Cu6(ipO)6(H2O)12] (4). Yield: 30% (based on Cu2+). Elemental analysis (%) calcd.: C, 28.97; H, 2.13. Found: C, 28.81; H, 2.05. IR (KBr disk, cm-1) selected bands: 3345 (w), 1596 (m), 1542 (m), 1445 (vs), 1366 (s), 1282 (m), 1155 (w), 1088 (w), 940 (m), 844 (m), 755 (vs), 632 (m). [Dy2Cu6(ipO)6(H2O)12] (5). Yield: 29% (based on Cu2+). Elemental analysis (%) calcd.: C, 28.87; H, 2.12. Found: C, 28.74; H, 2.24. IR (KBr disk, cm-1) selected bands: 3553 (w), 1597 (m), 1540 (w), 1445 (s), 1382 (m),1282 (w), 1162 (w), 1097 (w), 941 (w), 841 (w), 754 (s), 632 (w).

RESULTS AND DISCUSSION Single crystal X-ray diffraction studies reveal that CPs 1-2 are isostructural and crystallize in the triclinic P 1 space group, displaying a structure of 3D framework. Here 1 is selected as the representative example to describe the structure in detail. As shown in Figure 1, the asymmetric unit of 1 consists of four ipO3− ligands, two Sm(III) ions, four Cu(II) ions, six coordinated water molecules and one oxalate ion generated in situ. Each Sm(III) ion is eight-coordinated in distorted square anti-prismatic geometry by three aqua oxygen atoms, three carboxylic oxygen atoms from ligands and another two oxygen atoms from oxalate ion. The Sm-O bond lengths and the O-Sm-O bond angles are in the range of 2.386(4)-2.910(3) Å and 46.71(1)-154.47(1)°, respectively. The Cu(II) ions adopt two different coordination geometries. The Cu1, Cu2 and Cu3 adopt square pyramidal coordination geometry with the basal positions 7



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occupied by two carboxylic oxygen atoms and two phenolic oxygen atoms from two ligands and the Cu-O bonds lengths range from 1.879(3) to 1.953(3) Å. The apical positions are occupied by a phenolic oxygen atom (O8) from another ligand for Cu1, a carboxylic oxygen atom (O20) from another ligand for Cu2 and a carboxylic oxygen atom (O1) from another ligand for Cu3 to form weak Cu-O bonds with lengths of 2.650(4), 2.353(4) and 2.425(4) Å, respectively. The Cu4 exhibits a slightly distorted square-planar coordination geometry completed by two carboxylic oxygen atoms and two phenolic oxygen atoms from two ligands with the Cu-O bonds lengths ranging from 1.881(3) to 1.914(3) Å.

Figure 1. View of the local coordination environments of Sm(III) and Cu(II) ions in 1. Color scheme: black for C, red for O, blue for Cu and green for Sm.

Scheme 1. Coordination modes of ipO3- ligands in CPs 1-5. Color scheme: black for C, red for O, blue for Cu and green for Ln.

8


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Figure 2. View of the {Cu8} SBU in 1.

The ipO3- ligands in the asymmetric unit adopt η1:η1:η2:η1:η1-µ4 (I and II) and η1:η1:η3:η1:η1-µ5 (III) coordination modes in 1 (Scheme 1). With these modes, two Cu(II) ions are bridged by the phenol oxygen atoms of two ipO3- ligands to form a kind of planar [Cu2(ipO)2]2− unit. Two adjacent [Cu2(ipO)2]2− units are connected in face-to-face fashion to form a tetranuclear [Cu2(ipO)2]24− unit by weak Cu-Ocarboxylate bonds (2.353(4) and 2.425(4) Å). Two adjacent tetranuclear units interact with each other through two weak Cu-Ophenol bonds (2.650(4) Å) and π-π interactions between the phenyl rings (centroid-to-centroid distances: 3.548(5) Å), giving a type of multi-layered {Cu8} SBUs (Figure 2). The {Cu8} SBUs are further connected to adjacent ones by Sm(III) ions through the coordination of carboxylic oxygen atoms of the ipO3- ligands, forming 2D layers extending in the ac plane (Figure 3a). In the b axis direction, the oxalate ions bridge two Sm(III) ions (Sm1 and Sm2) locating in different 2D layers in a η1:η1:η1:η1-µ2 coordination mode, forming {Sm2} SBUs with the Sm1···Sm2 distance of 6.256(7) Å. The adjacent 2D layers are thus joined together through the oxalate ions, giving rise to the final 3D framework based on {Cu8} and {Sm2} SBUs (Figure 3b). A better insight into the feature of this intricate framework can be achieved by the application of a topological approach. As shown in Figure 4a and 4b, each {Cu8} SBU is connected to ten {Sm2} SBUs while each {Sm2} SBU is 9



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connected to five {Cu8} SBUs. If {Cu8} and {Sm2} SBUs are considered as 10-connected and 5-connected nodes from the topological point of view, respectively, this framework can be described as 5,10-connected MoGe2 topology with the total point symbol of {410}2{428·616·8} (Figure 4c). As far as we know, the CPs with this topology is extremely rare.42

Figure 3. (a) The 2D layer extending in the ac plane for 1. (b) The 3D framework composed of 2D layers and oxalate ions viewed from c axis direction for 1.

Figure 4. (a) (b) Polyhedral/topological representation of the {Cu8} (sky blue) and{Sm2} (yellow) SBUs. (c) Schematic representation of the (5,10)-connected net. 10


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Figure 5. View of the local coordination environments of Gd(III) and Cu(II) ions in 3. Color scheme: black for C, red for O, blue for Cu and green for Gd.

Figure 6. View of the {Cu6} SBU in 3.

The CPs 3-5 are isostructural. They crystallize in the triclinic system with a space group of P 1 as 1 and 2, but they exhibit a kind of chain structure. Here 3 is selected as the representative example to depict the structure in detail. As shown in Figure 5, the asymmetric unit of 3 is made of three ipO3− ligands, one Gd(III) ion, three Cu(II) ions, as well as six coordinated water molecules. The Gd(III) ion is eight-coordinated in distorted trigonal dodecahedron geometry by three carboxylic oxygen atoms from ipO3- ligands and five aqua oxygen atoms. The Gd-O bonds lengths range from 2.374(4) to 2.922(4) Å and the O−Gd−O bond angles are in the range of 46.72(1)-148.61(2)°. All of the Cu(II) ions adopt square-pyramidal coordination geometry with the basal positions occupied by two carboxylic oxygen atoms and two phenolic oxygen atoms from two ipO3- ligands, the Cu-O bonds lengths are in the range of 1.874(4)-1.931(4) Å. The difference is that the apical positions are occupied 11



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by a phenolic oxygen atom (O13) from another ligand for Cu1, an aqua oxygen atom (O21) for Cu2, and a carboxylic oxygen atom (O6) from another ligand for Cu3 (Cu1–O13: 2.845(2) Å, Cu2–O21: 2.520(6) Å, Cu3–O6: 2.770(5) Å). The ipO3ligands adopt three coordination modes of η1:η1:η3:η1-µ4 (IV), η1:η2:η2-µ3 (V) and η1:η2:η2:η1-µ3 (VI), which are all different from those in 1 (Scheme 1). Cp 3 also features [Cu2(ipO)2]2− units similar to those in 1. Three [Cu2(ipO)2]2− units in 3 are linked together to form a kind of multi-layered {Cu6} SBUs (Figure 6) through weak Cu-O bonds (Cu-Ophenol: 2.845(5); Cu-Ocarboxylate: 2.770(5) Å) and π-π interactions with the centroid-to-centroid distances of 3.794(4) and 3.585(3) Å. The adjacent {Cu6} SBUs are further linked by two Gd(III) ions which are coordinated by the carboxylic oxygen atoms of ipO3- ligands in the {Cu6} SBUs, giving rise to a chain structure along b axis as shown in Figure 7.

Figure 7. Chain structure composed of {Cu6} SBUs and Gd(III) ions for 3.

It can be seen from the above discussion that the reaction of H3ipO ligand with Cu(II) and Ln(III) salts under the same hydrothermal conditions afforded two types of CPs with a structural variation from 3D framework (type I) for 1-2 to 1D chain (type II) for 3-5. Indeed, there is a similar structural feature between the two types of CPs, that is, the phenol oxygen atoms of two ipO3- ligands bridge two Cu(II) ions to generate [Cu2(ipO)2]2− units which are further linked together by weak Cu-O bonds and π-π interactions to form multi-layered Cu-SBUs. However, the reaction involving in 12


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Sm(III) or Eu(III) ions led to the in situ generation of oxalate ligands, while those of Gd(III), Tb(III), and Dy(III) ions do not. In type I, the η1:η1:η1:η1-µ2 oxalate ligands bridge the Ln(III) ions to form {Ln2} SBUs, which further link the {Cu8} SBUs into the final 3D frameworks. Therefore, the generation and coordination of oxalate ions might be the key factor making the structure of type I differ from that of type II. The oxalate ions may arise from the partly decomposition of the carboxylic acid ligand of H3ipO, as the performances of other carboxylic acid ligands reported.43-47 The structural variation of 3d-4f coordination polymers along with the lanthanide series has been reported in the literatures.29,47-49 Although the structures of the compounds in those cases varied, they bear still the same organic ligands as used and their structural variation was ascribed to the lanthanide contraction effect. Obviously, the structural variation in our case of this work is dissimilar from those reported. It can be attributed to the different reactions of H3ipO ligand induced by lanthanide ions. However, the detailed decomposition mechanism of H3ipO ligand remains unknown, and needs further investigation. Thermal Analysis and PXRD patterns The crushed single-crystal sample was heated up to 850 °C in N2 atmosphere at a heating rate of 10 °C min-1. The TG curves show that five CPs undergo two kinds of weight loss processes because of the isomorphic feature of 1-2 and 3-5, respectively (Figure S1). The first weight losses of 1 and 2 in the range of 30-125 °C are 8.06% and 7.96%, respectively, corresponding to the losses of coordinated water molecules (calcd.: 7.37% for 1 and 7.35% for 2). The second weight losses of 4.88 % in the range of 126-323 °C for 1 and 4.74 % in the range of 126-318 °C for 2 can be 13



attributable to the pyrolysis of oxalate ions (calcd.: 5.99% for 1 and 5.78% for 2). The followed is the collapse of the frameworks with a series of complicated weight losses. The TG curve of 3 shows that the coordinated water molecules were gradually lost in the range of 30-282 °C (calcd./found: 10.55/10.88%). The weight loss above 282 °C is due to the decomposition of ipO3- ligands and the collapse of the frameworks. The TG curves of 4 and 5 are similar to that of 3. Their weight losses of coordinated water molecules are 11.23 % (calcd.: 10.85%) in the range of 30-286 °C for 4 and 11.39% (calcd.: 10.82%) in the range of 30-290 °C for 5. The TG results of CPs 1-5 agree well with their formulas, respectively. The PXRD experimental and computer-simulated patterns of CPs 1-5 are shown in Figure S2. The PXRD patterns of the bulk samples match their simulated patterns from the single-crystal structures, demonstrating the phase purity. Magnetic Property (b)

(a)

18

35 30

15

25

12

M / Nβ

3

-1

χ mT / cm mol K

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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20 15

9 6

10

1

2

3

4

1

5

2

3

4

5

30

40

50

3

5 0

0 0

50

100

150

200

250

300

0

10

20

H / kOe

T /K

Figure 8. (a) The plots of χmT versus T for 1-5 recorded at a dc field of 1 kOe. (b) The plots of M versus H for 1-5 in the field range of 0-50 kOe at 2 K.

The magnetic susceptibilities of 1-5 have been studied in the range of 300-2 K with an applied direct current magnetic field of 1 kOe (Figure 8a). The room temperature χmT values of 1-5 are 3.29 (1), 5.51 (2), 21.15 (3), 27.20 (4) and 35.5 (5) cm3 mol-1 K, 14


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respectively. The experimental and theoretical values of 1 are very close. The experimental values of other CPs are a little higher than the corresponding expected values (Table S1), which may be ascribed to the unquenched first-order orbital momentum of Ln(III) ions.50 As the temperature was lowered, the χmT values of 1 and 2 almost decrease in linear trend to reach the minimum of 0.21 and 0.05 cm3 mol-1 K at 2 K, respectively. The decreases may be due to antiferromagnetic interactions and/or depopulation of the Stark sublevels.51,52 The χmT value of 3 decreases slowly to a value of 19.00 cm3 K mol−1 at 7 K and then decreases sharply to reach a minimum of 14.39 cm3 K mol−1 at 2 K. The weak antiferromagnetic interactions between the metal centers (θ = -0.61 by Curie-Weiss fitting, Figure S3) and/or the zero-field splitting of the ground states may led to this result.21 For 4, the χmT value increases gradually to reach a maximum of 29.72 cm3 K mol−1 at 22 K and then decreases abruptly to a value of 25.22 cm3 K mol−1 at 2 K. The first increase of the χmT value above 22 K reveals the possible ferromagnetic interactions in the system (θ = 3.64 by Curie-Weiss fitting, Figure S4), while the decrease below 22K demonstrates the depopulation of the Stark levels of Tb(III) ions.17 The χmT value of 5 decreases smoothly to 16.93 cm3 K mol-1 at 120 K then increases slowly to a maximum of 17.13 cm3 K mol-1 at 45 K, following by an abruptly decrease to 12.73 cm3 K mol-1 K at 2 K. The crystal-field effects and/or large orbital momentum with strong spin-orbit coupling for Dy(III) ions might be responsible for the first decrease of the χmT value as the temperature decreases though the Curie-Weiss fitting between 120-300 K gives a negative θ value (θ = -3.54, Figure S5).21,53 The increase of the χmT value below 120 K evidences the

15



existence of possible weak ferromagnetic interactions.53-55 As for the final decrease of χmT value, it indicates the depopulation of Stark levels for Dy(III) ions. (b)

(a)

14

15

12 -1

18

10

5.0 T 4.5 T 4.1 T 3.5 T 3.0 T 2.4 T 2.0 T 1.5 T 1.0 T 0.5 T

-1

12

-∆ Sm / J kg K

M / Nβ

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 27

2K 3K 4K 5K 6K 7K 8K

9 6 3 0 0

10

20

30

40

50

8 6 4 2 0 2

3

4

H / kOe

5

6

7

8

9

T/K

Figure 9. (a) The plots of M versus H for 3 in the field range of 0-50 kOe at 2-8 K. (b) −∆Sm of 3 in the field range of 0-50 kOe at 2-8 K.

The field dependence of the magnetization (M) for 1-5 was performed in the field (H) range of 0-50 kOe at 2 K. As shown in Figure 8b, the M values of 1 and 2 increase slowly with the increasing H and reach 0.27 and 0.12 Nβ at 50 kOe, respectively. While the M values of 4 and 5 increase relative rapidly at low field and reach 17.25 and 14.32 Nβ at 50 kOe, respectively. These values are all lower than the corresponding theoretical saturated values (Table S1), respectively, suggesting the presence of the low-lying excited states and/or large magnetic anisotropy of Ln(III) ions.56-58 For 3, the M value exhibits a steadily increase with the increasing H and lacks of saturation even when the H reach 50 kOe. The M value of 16.79 Nβ at 50 kOe is far from the theoretical saturated value, indicating the presence of the low-lying excited states (Table S1).21 In view of the presence of Gd(III) ions with large spin ground state and isotropic, which are advantageous for MCE, the field dependence of the magnetization of 3 in the range of T = 2.0-8.0 K and H = 0-50 kOe (Figure 9a) were further performed and the magnetic entropy changes (−∆Sm) were calculated 16


Page 17 of 27

using the Maxwell equation as follows: −∆Sm(T) = ∫[∂M(T,H)/∂T]HdH.59,60 The −∆Sm value reaches a maximum of 13.97 J kg−1 K−1 for ∆H = 50 kOe at 4.0 K (Figure 9b). Perhaps as the presence of antiferromagnetic interactions and the crystal field effect, this value is smaller than the theoretical value of 34.81 J kg−1 K−1 calculated for uncoupled six Cu(II) and two Gd(III) ions.61 However, it is comparable to those of Cu-Gd CPs reported in the documents.21,22

0.05

1 0

0.00

-1 2

4

6

8

10

2.0 1.5

0.4 -1

-1

Hdc = 2 kOe

0.3

3

2.5

0.2

1.0

0.1

0.5

0.0

2

4

T /K

6

8

χ '' /cm mol

2

0.10

0.5 32 Hz 70 Hz 100 Hz 324 Hz 550 Hz 775 Hz 885 Hz

3

3

3

0.15

3.0

χ ' / cm mol

Hdc = 0 kOe

4

-1

5 -1

(b)

0.20 32 Hz 70 Hz 100 Hz 324 Hz 550 Hz 775 Hz 885 Hz

3

6

χ '' /cm mol

(a)

χ ' /cm mol

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


10

T /K

Figure10. The temperature dependence of ac susceptibility at indicated frequencies for 5 under 0 Oe (a) and 2 kOe (b) dc field.

To further investigate the dynamics of magnetization of CPs 3-5, the alternating current (ac) magnetic measurements have been performed under a 2.5 Oe ac field and a 0 Oe dc field for variable frequencies. No frequency dependence is observed in the in-phase (χ′) and out-of-phase (χ″) plots of 3 and 4 above 2 K (Figure S6). Both the in-phase (χ′) and out-of-phase (χ″) signals of 5 show frequency dependence, and the out-of-phase (χ″) signals reveal plateaus in the temperature range of 5.0-7.0 K (Figure 10a). This phenomenon may be that the quantum tunneling of the magnetization (QTM) in 5 reduces the energy barrier (Ueff) and influences the slow relaxation partially. Thus the ac susceptibilities of 5 were further measured in the presence of a 2.5 Oe ac field and a static dc field of 2 kOe to weaken the possible QTM. As 17



expected, the QTM is partially suppressed, both the in-phase (χ′) and out-of-phase (χ″) signals display frequency dependence and clear out-of-phase (χ″) peaks appear in the temperature range of 4.0-8.0 K (Figure 10b), indicating the presence of field-induced slow magnetic relaxation at low temperature. The temperature dependence of the relaxation time can be described by the Arrhenius law, τ = τ0exp(Ueff/kBT), and the best fit affords energy barrier Ueff = 63.68 K and pre-exponential τ0 = 3.77 × 10-8 s (Figure 11a), which is consistent with the expected value of 10-6-10-11 for a SMM.62,63 In the temperature range of 5.0-7.0 K with a 2 kOe dc field, the Cole-Cole plots exhibit semicircular shapes (Figure S7). The best fits to the experimental data by a generalized Debye model afford α value of 0.16-0.23, indicating a single relaxation process. To obtain further confirmation of the slow magnetic relaxation behavior of 5, additional dc magnetization measurement at 2 K was performed. The curve shows hysteresis with a small coercive field about 14 Oe and a small remnant magnetization of 0.04 Nβ (Figure11b). In the hysteresis loop, the steps due to faster relaxation via resonant QTM is not so clear as other Ln CPs.64 (b)

16 12

-6.0

8

-6.5

4

M / Nβ

-5.5

-7.0 -7.5

Ueff = 63.68 K

-8.0

-8

-8.5

τ = 3.77 * 10 s

-9.0 0.13 0.14 0.15 0.16 0.17 0.18 0.19 0.20

T

-1

T =2K

0

0.3 0.2

-4 M/Nβ

(a) -5.0

ln(τ )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 27

-8

0.0

-0.2

-12 -16 -60.0

0.1

-0.1 -0.3

-0.08 -0.04 0.00 0.04 0.08

H / kOe

-40.0

-20.0

-1

0.0

20.0

40.0

60.0

H / kOe

/K

Figure 11. (a) ln(τ) versus T-1 plot for 5 under a 2.5 Oe ac field and a 2 kOe dc field. The solid line represents Arrhenius fit of the frequency-dependent data. (b) Hysteresis loop of 5 at 2 K and the expansion of hysteresis region (inset). 18


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The above magnetic determination indicates that these CPs display different magnetic properties, and only 5 shows SMM behaviors. Obviously, the structural parameters of the CPs in the same type are very close as their isostructural feature (Table S2-S6). Thus the inherent magnetic anisotropy of the Dy(III) ions and the ferromagnetic interactions in the system might be the main factors contributing to the field induced SMM behaviors of 5.65,66 On the other hand, it should be mentioned that the relative orientation of the local axes for Dy(III) ions in the chain structure of 5 may also affect the magnetic anisotropy of the system, benefiting for the high energy barrier against the spin reversal.66,67

CONCLUSION Two types of Cu-Ln heterometallic CPs with H3ipO were synthesized under the same hydrothermal conditions. The structures of the CPs change from 3D framework with a (5,10)-connected MoGe2 topology based on {Cu8} and {Ln2} SBUs to chain structure built up from {Cu6} SBUs and Ln(III) ions. The weak Cu-O bonds and π-π interactions help to form the multi-layered Cu-cluster SBUs of the CPs. The structural variation of the CPs along with the lanthanide series was ascribed to the different reactions of H3ipO ligand induced by lanthanide ions. The static magnetic properties of all CPs and dynamic magnetic properties of 3-5 have been studied. CP 3 displays MCE with the maximum −∆Sm value of 13.97 J kg-1 K-1 for ∆H = 50 kOe at 4.0 K and 5 display field induced SMM behaviors with an energy barrier Ueff = 63.68 K and pre-exponential τ0 = 3.77 × 10−8 s. This work demonstrates not only an example of synthesizing 3d-4f heterometallic CPs with different structures via different reactions 19



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Page 20 of 27

of ligand induced by lanthanide ions, but also an example of using the ligand with only O-donors to obtain 3d-4f heterometallic CPs with rare topological structure and interesting magnetic properties.

ASSOCIATED CONTENT Supporting Information TGA curves (Figure S1), PXRD patterns (Figure S2), additional magnetic data (Figures S3−S7 and Table S1), selected bond lengths and angles (Table S2-S6) and X-ray crystallographic files (CIF) for 1−5. This information is available free of charge via the Internet at http://pubs.acs.org.

ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (21271050

and

21261004)

and

Guangxi

Natural

Science

Foundation

(2013GXNSFGA019008 and 2014GXNSFBA118055).

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For Table of Contents Use Only

Two types of Cu-Ln Heterometallic Coordination Polymers with 2-Hydroxyisophthalate: Syntheses, Structures and Magnetic Properties Kai Wang,†,‡ Zi-Lu Chen,‡ Hua-Hong Zou,‡ Zhong Zhang,‡ Wei-Yin Sun,† Fu-Pei Liang∗,‡,§ E-mail address: [email protected] (F. Liang)

Synopsis: Two types of Cu-Ln heterometallic coordination polymers were synthesized under the same hydrothermal conditions. Their structures display a variation from 3D framework with a rare MoGe2 topology based on {Cu8} SBUs and {Ln2} SBUs for type I to chain structure based on {Cu6} SBUs and mononuclear Ln(III) ions for type II. 3 shows MCE and 5 shows SMM behaviors.

27


Two Types of Cu-Ln Heterometallic Coordination ... - ACS Publications

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