A Series of CuIIâLnIII MetalâOrganic Frameworks Based on 2,2

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A Series of CuII-LnIII Metal-Organic Frameworks Based on 2,2’-Bipyridine-3,3’-dicarboxylic Acid: Syntheses, Structures and Magnetic Properties Ke Liu, Jing-Min Zhou, Hui-Min Li, Na Xu, and Peng Cheng Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg5012617 • Publication Date (Web): 27 Oct 2014 Downloaded from http://pubs.acs.org on November 3, 2014

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Crystal Growth & Design

A Series of CuII-LnIII Metal-Organic Frameworks Based on 2,2’-Bipyridine-3,3’-dicarboxylic Acid: Syntheses, Structures and Magnetic Properties Ke Liu, Jing-Min Zhou, Hui-Min Li, Na Xu* and Peng Cheng* Department of Chemistry and Key Laboratory of Advanced Energy Material Chemistry (MOE), Nankai University, Tianjin 300071, P. R. China; and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China ABSTRACT: A series of CuII-LnIII heterometallic metal-organic frameworks (HMOFs), displaying three types of structures with the formulae of {[Ln2Cu(BDPC)4(H2O)6]·9H2O}n (Ln = La,

1;

Pr,

2;

Nd,

3;

BPDC2-

=

2,2’-bipyridine-3,3’-dicarboxylate),

{[Ln2Cu2(BPDC)5(H2O)6]·9H2O}n (Ln = Pr, 4; Nd, 5; Sm, 6; Eu, 7; Gd, 8; Tb, 9) and [DyCu3(BPDC)4(NO3)(H2O)6]n (10), have been successfully synthesized and well characterized. Single crystals available for X-ray diffraction measurements were carried out for MOFs 3, 7, 9 and 10. PXRD and FT-IR analysis demonstrates the isomorphrsm for MOFs 1-3, as well as MOFs 4-9. The BPDC2- ligand herein exhibits seven different coordination modes to link metal centers for the construction of different three-dimensional (3D) structures. The structures of the three types of CuII-LnIII HMOFs can be described topologically with Schläfli symbol {3·62}{32·66·73·83·9}{62·7},

{4·62}2{42·64·86·103}{6·82}2,

and

ACS Paragon Plus Environment

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{4·8·9}2{6·8·9}2{6·82·93}{82·9}2, of which the latter two are new topologies. The static magnetic properties of the ten HMOFs and dynamic magnetic properties of 9-Tb2Cu2 and 10DyCu3 have been studied. Introduction Metal-organic frameworks (MOFs) have attracted increasing attention in the past decades as an emerging class of porous materials which are composed of metal-containing nodes and organic linkers.1-4 The porous nature and chemically tunable selectivity make MOFs promising materials for gas storage,5-8 separation9-13 and catalysis14-17. More recently, a variety of new applications for MOFs have also been developed in the fields of sensing,18,19 optics,20-23 pollutant sequestration,24,25 photonic and electronic devices,26 drug release,27 etc. Versatile functionalities originate from the combination of inorganic metal centers and organic ligands that provided high degree of synthetic diversity, rational designed ordered structures and properties.29-33 The study of 3d-4f heterometallic MOFs is one of the most prosperous issues in this field because the fascinating topologies and multiple properties can be achieved from different chemical and physical natures of the two types of metal ions.34 Although lots of 3d-4f heterometallic complexes have been synthesized and well characterized in recent years,35-41 it is still a big challenge for chemical researchers to rationally synthesize this kind of compounds. The significant differences in nature between transition metal and lanthanide lead to competitive coordination between them to the same ligand during synthesis. In general cases, simply mixing them together would prefer to produce alternative homometallic complexes.42 Based on hard and soft acids and bases (HSAB),43 a useful and widely used synthetic strategy towards heterometallic systems is to employ multidentate ligands that are elaborately designed to possess


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different coordination donors for both 3d and 4f metal ions, namely N and O atoms.44,45 From this point of view, pyridine-carboxylic acids containing Npyridine and Ocarboxyl groups as functionalities have been considered as one family of excellent ligands to synthesize heterometallic complexes and employed successfully by our group.46-52 In previous studies, we employed ligand 2,2’-bipyridine-3,3’-dicarboxylic acid (H2BPDC)

to isolate homometallic

Ln(III)-MOFs53,54 and heterometallic Co(II)-Ln(III) MOFs.55 In this paper, ten Cu(II)-Ln(III) heterometallic MOFs: {[Ln2Cu(BDPC)4(H2O)6]·9H2O}n (Ln = La, 1; Pr, 2; Nd, 3; BPDC2- = 2,2’-bipyridine-3,3’-dicarboxylate), {[Ln2Cu2(BPDC)5(H2O)6]·9H2O}n (Ln = Pr, 4; Nd, 5; Sm, 6; Eu, 7; Gd, 8; Tb, 9) and [DyCu3(BPDC)4(NO3)(H2O)6]n (10) were successfully synthesized via the N,O-ligand approach and structurally characterized. These heterometallic MOFs showed three types

of 3D frameworks

{3·62}{32·66·73·83·9}{62·7},

with

topologies

of the short

(Schläfli) symbols

{4·62}2{42·64·86·103}{6·82}2,

and

{4·8·9}2{6·8·9}2{6·82·93}{82·9}2, respectively. The latter two topologies are new in MOF chemistry. The static magnetic properties of the ten HMOFs and dynamic magnetic properties of 9-Tb2Cu2 and 10-DyCu3 have been studied. 8-Gd2Cu2 shows magnetocaloric effect (MCE) with −∆Sm value of 22.05 J Kg-1 K-1 at 2 K and ∆H = 7 T. However, there are no χ’’ signals for both 9 and 10 complexes in zero field above 1.8 K, suggesting the absence of slow relaxation.

Experimental Section Materials and Methods. H2BPDC and Ln(OH)3 were obtained by the literature method,56 and the other reagents were purchased commercially and used without further purification. Elemental analyses for C, H and N were performed on a Perkin-Elmer 240 CHN elemental analyzer.


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Fourier Transform infrared (FT-IR) spectra (KBr pellets) were recorded in the range 400-4000 cm-1 on a Bruker TENOR 27 spectrophotometer. Powder X-ray diffraction (PXRD) patterns were obtained on a Rigaku D/Max-2500 X-ray diffractometer (Cu-Kα). Magnetic measurements were carried out on a Quantum Design SQUID MPMS VSM magnetometer. Microcrystalline samples are ground into powder, put into sample holders and fixed by adding eicosane. Diamagnetic corrections were evaluated from Pascal’s constants for all the atoms and sample holders. Single-crystal X-ray Measurements and Structure Characterization. Single crystals of 3, 7, 9 and 10 available for X-ray diffractions were measured at 123(2) K to determine their structures. The measurements were performed on a Agilent Technologies SuperNova Single-Crystal Diffractometer with graphite-monochromatic Mo-Kα radiation (λ = 0.71073 Å) by ω scan mode. All the structures were solved by direct methods with SHELXS, and all non-hydrogen atoms are refined by full matrix least-squares techniques with anisotropic thermal factors using SHELXL. The hydrogen atoms are fixed by using riding mode and treated isotropically with the program package Olex2.57,58 The content of large voids contained in structures of 3, 7 and 9 are removed with the SQUEEZE program. The crystal parameters and refinement results are listed in Table 1, and selected bond and angle parameters are listed in Table S2. Synthesis of 1-3. Ln(OH)3 (0.4 mmol), Cu(NO3)2·3H2O (0.1 mmol) and H2BPDC (0.6 mmol) were put into a mixed solvent (8 mL H2O/2 mL EtOH) and sealed in a 25 mL Teflon-lined stainless autoclave after stirring for several minutes. The autoclave was heating at 130 °C for three days and slowly cooled to room temperature at the rate of 2 °C / h. Green needle-like crystals of 3 were obtained which are available for single crystal X-ray diffraction measurement. Microcrystalline samples of 1 and 2 are also collected. The similar FT-IR spectra and PXRD


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patterns of microcrystal samples 1 and 2 demonstrate their isostructuralism with 3. Yield: ca. 30% based on Cu(NO3)2·3H2O. Elemental analysis Found (calcd) for La2CuC48H54N8O31 (1): C, 36.44 (36.48), H, 3.09 (3.44), N, 6.96 (7.09); IR (cm-1) for 1: 3272(br), 1599(vs), 1400(s), 1160(m), 1098(m), 880(m), 783(s), 708(m), 639(m), 530(s), 434(m). Pr2CuC48H54N8O31 (2): C, 36.23 (36.39), H, 2.92 (3.44), N, 6.97 (7.07); IR (cm-1) for 2: 3267(br), 1593(vs), 1401(s), 1159(m), 1101(m), 877(m), 785(s), 705(m), 635(m), 535(s), 433(m). Nd2CuC48H54N8O31 (3): C, 36.02 (36.24), H, 2.94 (3.42), N, 6.93 (7.04). IR (cm-1) for 3: 3263(br), 1592(vs), 1405(s), 1162(m), 1097(m), 870(m), 784(s), 710(m), 636(m), 532(s), 427(m). Synthesis of 4-9. The preparation process of 4-9 was simillar to the method as described above. Green flaky crystals of 7 and 9 suitable for single crystal analyses were obtained, while only microcrystalline powders of 4, 5, 6, and 8 were obtained by filtration, washing, and airdrying. It is notable that the products of 2-Pr2Cu and 4-Pr2Cu2 were obtained in the same reaction autoclaves, as well as 3-Nd2Cu and 5-Nd2Cu2. Different appearances were the ways to differentiate them, as shown in Scheme 1. The FT-IR spectra and PXRD patterns of 4-9 demonstrate their isostructuralism. Yield: ca. 35%, 40%, 50%, 40%, 25% and 27% for 4-9 based on Cu(NO3)2·3H2O. Elemental analysis Found (calcd.) for Pr2Cu2C60H60N10O35 (4): C, 38.65 (38.13), H, 3.61 (3.20), N, 7.45 (7.41); IR (cm-1) for 4: 3241(br), 1608(vs), 1404(s), 1163(m), 1101(m), 869(m), 770(s), 705(m), 646(m), 527(s), 436(m). Nd2Cu2C60H60N10O35 (5): C, 38.47 (37.99), H, 3.79 (3.19), N, 7.50 (7.38); IR (cm-1) for 5: 3251(br), 1609(vs), 1405(s), 1158(m), 1096(m), 869(m), 771(s), 707(m), 643(m), 528(s), 433(m). Sm2Cu2C60H60N10O35 (6): C, 38.15 (37.75), H, 3.17 (3.17), N, 7.33 (7.33); IR (cm-1) for 6: 3245(br), 1614(vs), 1401(s), 1162(m), 1099(m), 871(m), 772(s), 705(m), 644(m), 527(s), 432(m). Eu2Cu2C60H60N10O35 (7): C, 38.17 (37.69), H, 3.53 (3.16), N, 7.37 (7.33); IR (cm-1) for 7: 3241(br), 1610(vs), 1404(s), 1157(m),


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1100(m), 869(m), 770(s), 707(m), 643(m), 530(s), 433(m). Gd2Cu2C60H60N10O35 (8): C, 38.02 (37.48), H, 3.19 (3.14), N, 7.28 (7.28); IR (cm-1) for 8: 3250(br), 1608(vs), 1402(s), 1160(m), 1095(m), 869(m), 773(s), 705(m), 647(m), 530(s), 435(m). Tb2Cu2C60H60N10O35 (9): C, 38.14 (37.41), H, 3.01 (3.13), N, 7.43 (7.27). IR (cm-1) for 9: 3249(br), 1612(vs), 1405(s), 1159(m), 1091(m), 869(m), 772(s), 709(m), 641(m), 535(s), 434(m). Synthesis of 10. Similar preparation process as described above was performed to synthesize complex 10. Blue-green block crystals were obtained with yield of ca. 20% based on Cu(NO3)2·3H2O. Elemental analysis Found (calcd.) for DyCu3C48H36N9O25 (10): C, 38.52 (38.64), H, 2.65 (2.43), N, 8.34 (8.45). IR (cm-1): 3416(br), 1597(vs), 1388(s), 1109(s), 779(m), 623(s), 440(w).

Scheme 1. Different shapes of crystals for the three types of Ln-Cu MOFs.

Table 1. Crystal parameters and refinement details for complexes 3, 7, 9 and 10

Compounds

3

7

9

10

Formula

Nd2CuC48H42N8O25

Eu2Cu2C60H60N10O35

Tb2Cu2C60H60N10O35

DyCu3C48H36N9O25

Fw

1591.0

1912.18

1926.11

1491.98

Temp / K

122.8(5)

120.0

125.1(2)

124.60(10)

Crystal type

needle-like

flaky

flaky

block

Crystal system

Tetragonal

Monoclinic

Monoclinic

Triclinic

Space group

I41/a

P21/c

P21/c

P-1

a, Å

45.3447(7)

11.2835(3)

11.2520(10)

12.1832(9)


6

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b, Å

45.3447(7)

22.3634(7)

22.3034(9)

14.8529(9)

c, Å

11.2994(3)

27.3143(14)

27.1573(15)

15.1970(9)

α, deg

90.00

90.00

90.00

92.957(5)

ß, deg

90.00

99.148(4)

98.299(6)

105.125(6)

γ, deg

90.00

90.00

90.00

110.694(6)

V, Å3

23233.2(7)

6804.8(4)

6744.0(8)

2451.8(3)

Z

16

4

4

2

Dc, g/cm3

1.687

1.849

1.879

2.021

µ, mm-1

2.212

2.540

2.800

2.896

Rint

0.0400

0.0501

0.0437

0.0656

F(000)

11632.0

3744.0

3760.0

1476.0

GOF on F2

1.017

1.059

1.065

1.025

R1, wR2 [I>2σ(I)]

0.0391, 0.0825

0.0592, 0.1203

0.0708, 0.1784

0.1136, 0.2738

R1,wR2(all data)

0.0621, 0.0892

0.0981, 0.1501

0.0854,0.1908

0.1268, 0.2825

Results and Discussion Crystal Structure of {[Ln2Cu(BPDC)4(H2O)6]·9H2O}n (Ln = La (1); Pr (2) and Nd (3). PXRD and FT-IR analysis demonstrates that 1-3 are isomorphous, and the structure of 3 is determined by single crystal X-ray diffraction and described representatively. Complex 3 crystallizes in tetragonal space group I41/a. As shown in Figure 1a, the asymmetric unit of 3 contains two crystallographiclly independent Nd3+ ions, one Cu2+ ion and four BPDC2- aions. Both Nd3+ ions are nona-coordinated, and their coordination spheres are completed by six Ocarbxoyl atoms from four doubly-deprontoned BPDC2- ligands together with three Oaqua (water molecules). The coordnation geometry of Nd3+ ions can be best decribed as a distroted monocapped square antiprism, where O8 for Nd1 and O3A for Nd2 are serving as capping atoms


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(Figures 1b and c). The lengths of all the Nd-O bonds are in the range of 2.404(6)-2.671(6) Å. The Cu2+ ion is chelated by three paris of N2 pockets from three BPDC2- ligands, exhibiting a distorted octahedral geometry. The lengths of Cu-N bonds are in the range of 2.003(7)-2.403(7) Å.

Scheme 2. Coordination modes of ligand BPDC2- showing in 1-10.

Figure 1. (a) The coordination environments around metal ions in 3, H atoms and guest water molecules are omitted for clarity. (b) The mono-capped square antiprismatic coordination spheres of Nd1 and Nd2 in 3. The four BDPC2- ligands contained in one asymmetric unit adopt three coordination modes (Scheme 2 A-C). As shown in Figure S1, the two Nd3+ ions are bridged into binculear units through two BPDC2- ligands which use two carboxylate groups in µ2-η1:η1:η1:η1 (mode A) and one carboxylate in µ2-η1:η1 fashion (mode B), respectively. Each of the BPDC2- ligands capture one Cu2+ ion by its N2 donor sites. The nearest distances between Nd1···Nd2, Nd1···Cu1 and Nd2···Cu1 are 5.58, 6.79 and 8.66 Å. The Nd2 units are linked into a 1D chain through two different types of BPDC2- ligands with mode B and C. The 1D neodymium chains are furhter connected to each other through CuN6 secondary building units (SBUs) to construct a 3D heterometallic framework (Figure 2). Apart from guest water molecules in the structure, the 3D framework exhibits 1D channels along the c direction. Excluding the vander Waals radius of channel wall atoms, the dimensions of the quadrangle channels are ~6.8 × 6.8 Å2.


8

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Figure 2. (a) View of the 1D channel in the structure of 3 along the c direction; (b) view of the 1D channel of 3 along the a direction; (c) view of the framework with 1D channels in the structure of 3 along the c direction. Color code: Nd, violet; Cu, blue; O, pink; C, green. Crystal Structure of {[Ln2Cu2(BPDC)5(H2O)6]·8H2O}n (Ln = Pr, 4; Nd, 5; Sm, 6; Eu, 7; Gd, 8; Tb, 9). XRD and FT-IR analysis revealed the isomorphism of 4-9, so only the structure of complex 9 is described. Complex 9 crystallizes in monoclinic space group P21/c. The asymmetric unit possesses two crystallographically independent Tb3+ ions, two Cu2+ ions and five BPDC2− ligands (Figure 3a). Both Tb1 and Tb2 are nonacoordinated, and their coordination environments are completed by three water molecules and six oxygen atoms from four BPDC2− ligands, showing a distorted single-capped square antiprism. O13 for Tb1 and O5 for Tb2 are acting as the capping atoms (Figure 3b). The Tb−O bond lengths are in the range of 2.326(5)2.728(6) Å. Both Cu1 and Cu2 exhibit distorted octahedral coordination geometry. Cu1 is surrounded by four nitrogen atoms (N1, N2, N5, N6) from three BPDC2− and two oxygen atoms (O17A, O28), while Cu2 is coordinated with six nitrogen atoms (N3A, N4A, N7, N8, N9, N10) from three BPDC2− to form distorted octahedral coordination geometry.

Figure 3. (a) The coordination environments around metal ions in 9, H atoms and guest water molecules are omitted for clarity. (b) The mono-capped square antiprismatic coordination spheres of Tb1 and Tb2 in 9. The five BPDC2- ligands in the asymmetric unit of 9 exhibit four different modes to coordinate Tb3+ and Cu2+ centers (Figure S2). Similar to the binuclear Nd2 subunit in the structure of 3, Tb1


9


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and Tb2 are bridged together through two BPDC2- ligands which empolys coordination mode of A and B, respectively, and further linked into 1D chain along the a direction via these two kinds of BPDC2- ligands. The distances of negibouring Tb3+ ions in the chain are 5.61 and 5.64 Å. On the other hand, the Cu2+ ions are also connected into pairs through a BPDC2- ligands in coordinaiton mode E and the distance between Cu1 and Cu2 is 11.53 Å. The Cu2 dimers and the Tb chains are interconnected by the four types of BPDC2- ligands to generate a 3D framework (Figure 4). Apart from the guest water molecules, the framework of 9 contains 1D channels along the a direction. The dimensions of the quadrangle channels are ~3.8 × 3.8 Å2 excluding vander Waals radius.

Figure 4. (a) View of the 1D channel of 9 along the a direction. (b) View of a 2D layer in the framework of 9 along the a direction. (c) Perspective view of the 3D framework of 9 along the a direction. Color code: Tb, violet; Cu, blue; O, pink; C, green. Crystal Structure of [DyCu3(BPDC)4(NO3)(H2O)6]n (10).

Figure 5. (a) The coordination environments around metal ions in 10, H atoms and guest water molecules are omitted for clarity. (b) The mono-capped square antiprismatic coordination spheres of Dy1 in 10. Single crystal X-ray data reveals that complex 10 crystallizes in triclinic space group P-1. The asymmetric unit of 10 comprises of three crystallographically independent Cu2+ ions, one Dy3+ ion, four BPDC2- ligands and one NO3- anion (Figure 5a). Dy1 adopts a slightly distorted square


10

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antiprism coordination geometry in which the central metal ion is surrounded by four Ocarboyxl atoms from four separate BPDC2− ligands and four Oaqua atoms (Figure 5b). The lengths of Dy−O bonds are in the range of 2.312(8)-2.482(4) Å. The three Cu2+ ions exhibit different coordination geometries. Cu1 is bound with two N atoms (N7, N8) from one BPDC2- ligand, one Ocarboxyl atom (O16) from another BPDC2- ligand, one Onitrate atom (O23) and one Oaqua atom (O22), forming a distorted square pyramid polyhedron. The coordination geometry of Cu2 is also square pyramid and the sphere around Cu2 is completed by four N atoms (N3, N4, N5, N6) from two BPDC2- ligands and one Ocarboxyl atom (O22A) from another BPDC2- ligand. Cu3 displays a distorted octahedral geometry whose equatorial positions are occupied by two N atoms (N1, N2), one Ocarboxyl atom (O7) and one Oaqua atom (O13) while two Ocarboxlate atoms (O2A, O6) from two separate BPDC2- ligands are in the apical positions. The four BPDC2- ligands in one asymmetric unit of 10 empoly three different coordination modes as shown in Figure S3. Dy1 and Cu2 ions are bridged through the carboxylate groups and N2 donors respectively from BDPC2- ligands in mode F, froming a 1D chain along the c direction. Furhtermore, Cu2 is bound to Cu3 and Cu1 through BPDC2- ligands in the fashion of mode F and E, respectively, while Dy1 is bonded with Cu3 via BPDC2- ligands which are exhibiting coordination mode G, generating a 3D framework structure (Figure 6).

Figure 6. (a) Perspective view of the 3D structure of 10. (b) View of the framework of 10 along the c direction and its 1D chain composed of Dy1 and Cu2. Color code: Dy, violet; Cu, blue; O, pink; C, green. Topology studies. In order to better understand the nature of these intricate frameworks, the topologies of the three types of MOFs are analyzed by program TOPOS.59 For 1-3, each Ln2


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dimer connecting to six BPDC2− ligands can be regarded as a 6-connected node, and each Cu2+ ion linking three BPDC2− ligands can be regarded as a 3-connected node. The BPDC2 – ligands with mode A and B are serving as 3-connected nodes while others showing mode C are linkers. According to the simplification principle, the structures of complexes 1-3 can be expressed as a 3,6-connected net with the point symbol {3·62}{32·66·73·83·9}{62·7}, which is already reported by our group previously19. For 4-9, each Ln2 dimer linking six BPDC2− ligands is considered as a 6-connected node, and each Cu2+ ion coordinated with three BPDC2− ligands is regarded as a 3-connected node. The BPDC2– liands with mode A and B are acting 3-connected nodes while the others exhibiting mode D and E are linkers. The structures of 4-9 can be simplified as a 3,3,3,6-connected net with the point symbol {4·62}2{42·64·86·103}{6·82}2, which is a new topology. For 10, each Dy3+ center linking with four BPDC2- ligands can be regarded as 4-connected node, and each Cu2+ ion bonding with three BPDC2- ligands can be treated as 3-connected node. BPDC2- ligands exhibiting mode F and G serve as 3-connected nodes and others with mode E act as

linkers.

The

structure

of

10

can

be

described

as

a

3,3,3,3,3,3,4-net

with

{4·8·9}2{6·8·9}2{6·82·93}{82·9}2. It is also a new topology.

Figure 7. Views of topological network of complexes 1-3 (a), 4-9 (b) and 10 (c). The nodes: Ln, violet; Cu, blue; ligands, green. Powder X-ray Diffraction (PXRD). The PXRD measurments have been performed on a Rigaku D/Max-2500 X-ray diffractometer at room temperature to confirm the purity of 3, 7, 9, 10, and the isomorphism of the two types of MOFs, (Figures S5-S7). The experimental patterns


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are in good agreement with the simulated peaks based on the single-crystal X-ray data, which are positive evidences of the high phase purity and isomorphism of the corresponding complexes. Magnetic Properties. The temperature dependence of the magnetic susceptibilities (χMT vs T) in the range of 2-300 K are measured by using microcrystalline samples of 1-10 at a static field of 1000 Oe, as shown in Figure 8. At room temperature (300 K), the χMT value of 0.39 cm3 K mol-1 for 1 is close to the expected value (0.38 cm3 K mol-1) for one spin-only Cu2+ ion (S = 1/2, g = 2) and two diamagnetic La3+ ions. The χMT values at room temperature for 2 and 3 are 2.98 (2-Pr2Cu), 1.04 (3-Nd2Cu) respectively, and the calculated values are 3.57 cm3 K mol-1 for 2 and 3.65 cm3 K mol-1 for 3 which are expected as the sum of the values of one spin-only Cu2+ ions and two Pr3+ ions (3H4, g = 4/5) for 2 and two Nd3+ ions (4I9/2, g = 8/11) for 3. The χMT values at room temperature for complexes 2 and 3 are lower than the calculated values for spinonly magnetic centers, indicating dominant antiferromagnetic interactions between metal ions. As shown in Figure 8, the magnetic behaviors of 1-3 are rather different. For 1 (La2Cu), the χMT product increases slightly upon cooling, reaching 0.45 cm3 K mol-1 at about 28 K and suggesting the presence of weak ferromagnetic interactions between Cu2+ ions. The χMT products are decreasing gradually to reach the minimum of 1.56 cm3 K mol-1 at 1.8 K for 2 and 0.74 cm3 K mol-1 at 8.5 K for 3, which are attributed to the thermal depopulation of the magnetic excited states arising from the lanthanide ions and/or the possible dominant antiferromagnetic interactions between metal ions.60,61 The χMT value for 3 then increases slightly when the temperature are continuously lowering to 1.8 K, further proving the presence of weak ferromagnetic interactions between Cu2+ ions.


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The χMT values at room temperature for complex 4-10 are 4.87 (4-Pr2Cu2), 4.35 (5-Nd2Cu2), 2.59 (6-Sm2Cu2), 4.76 (7-Eu2Cu2), 17.33 (8-Gd2Cu2), 26.18 (9-Tb2Cu2) and 17.79 (10-DyCu3) cm3 K mol-1, respectively. The experimental data are higher than the theoretical values as the sum of the values of two spin-only Cu2+ ions and two Ln3+ ions for 4-9 and three Cu2+ ions together with one Dy3+ ions for 10. The calculated χMT values at room temperature are 3.94 (4), 4.02 (5), 0.96 (6), 0.74 (7), 16.50 (8), 24.38 (9) and 15.28 (10), respectively. The deviations may be related to the unquenched first-order orbital momentum of Ln3+ ions.

Figure 8. Plots of χMT vs T curves for complexes 1-10. As the temperature was lowered, the χMT values of 4-10 decrease gradually to reach 2.12, 2.11, 0.74, 0.68, 16.65, 17.73 and 11.81 cm3 K mol-1 at 1.8 K. The fittings according to Curie-Weiss Law for these seven complexes all give negative θ values, related to the overall results combining the depopulation of Stark levels for Ln3+ ions and magnetic interactions between metal centers except complex 8. The small negative θ value -0.37 K for 8 suggests the presence of possible weak antiferromagnetic interactions.

Figure 9. Field-dependent magnetization plots at 2 K for complexes 1-10. The data of field dependence of magnetization (M) for complexes 1-10 has been collected at 2 K in the range of 0-70 kOe (Figure 9). The magnetization value of complex 1 is increasing gradually at low fields, and getting close to saturation at 70 kOe with the value of 1.06 Nβ, corresponding to S = 1/2 for 1-La2Cu and the weak ferromagnetic interactions between Cu2+ ions. Complex 8-Gd2Cu2 exhibits a similar M vs. H curve, and approaches the expected


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saturation value of 16 Nβ for S = 8. The magnetization values of the other nine complexes are increasing gradually with lacks of saturation even when the fields reach 70 kOe, indicating the presence of magnetic anisotropies and/or low-lying excited states of Ln3+ ions.62,63

Figure 10. (a) Field-dependent magnetization curves (M vs H) for complex 8-Gd2Cu2 at indicated temperatures. (b) −∆Sm values for 8-Gd2Cu2 as calculated by using the Maxwell relation. Gadolinium is widely used in molecular refrigerant materials, because large MCE can be favored by its 8S7/2 ground state, magnetic isotropy and weak superexchange interactions.64-66 The MCE effect of 8-Gd2Cu2 is evaluated by using the magnetization data with the method of the Maxwell relation −∆Sm(T) = ∫[∂M(T,H)/∂T]H dH.67-69 The field-dependent magnetizations within the range 2-10 K were further measured to calculate the magnetic entropy change (−∆Sm, Figure 9). The maximum −∆Sm value for the largest ∆H (from 7 T to 0 T) reaches 22.05 J Kg-1 K-1 at 2 K. The theoretical maximum of −∆Sm value for two Cu2+ (S = 1/2) and two Gd3+ (S = 7/2) ions is 23.98 J Kg-1 K-1 which is given by −∆Sm = R∑iln(2Si+1). The experimental value is smaller than the theoretical value, probably due to the presence of overall antiferromagnetic interactions, as well as crystal-field effect.70,71 Furthermore, considering the significant anisotropic nature of Tb3+ and Dy3+ ions, dynamic magnetic properties of 9-Tb2Cu2 and 10-DyCu3 were studied to expect SMM behaviors. The temperature-dependent ac susceptibilities of 9 and 10 were measured in the range of 2-20 K, however, no χM’’ signals were detected for both complexes (Figure S18). Conclusion


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In summary, three types of unreported 3d-4f CuII-LnIII heterometallic MOFs have been successfully synthesized by using solvothermal conditions with ligand 2,2’-bipyridine-3,3’dicarboxylic acid. The BPDC2- ligands in the ten MOFs display seven coordination modes to link metal centers, and give rise to different framework structures as the radius of lanthanide ion decreases. The frameworks of the three types of Ln-Cu MOFs can be expressed as {3·62}{32·66·73·83·9}{62·7},

{4·62}2{42·64·86·103}{6·82}2,

and

{4·8·9}2{6·8·9}2{6·82·93}{82·9}2. The latter two are new topologies. The static magnetic properties of the ten heterometallic MOFs and dynamic magnetic properties of 9-Tb2Cu2 and 10DyCu3 have been studied. Complex 8-Gd2Cu2 shows magnetocaloric effect (MCE) with −∆Sm value of 22.05 J Kg-1 K-1 at 2 K and ∆H = 7 T, and neither of the two complexes containing high anisotropic TbIII and DyIII ions show slow relaxation of magnetization in zero field above 1.8 K. Therefore, utilizing the ligand 2,2’-bipyridine-3,3’-dicarboyxlic acid which simultaneously contains N and O donor atoms to accommodate 3d and 4f metal ions, we have successfully synthesized a series of CuII-LnIII heterometallic MOFs with intriguing topologies and magnetic properties. ASSOCIATED CONTENT Supporting Information. Coordination modes of the ligand BPDC2- in the three structures (Figure S1-S3), FT-IR spectra (Figure S4), PXRD patterns (Figure S5-S7) , experimental and calculated values of magnetic behaviors (Table S1), curves of Currie-Weiss Fittings (Figures S8-17), plots of ac magnetic measurements of 9 and 10 (Figure S18), selected bond lengths and angles (Table S2) and X-ray


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crystallographic files (CIF) for 3, 7, 9 and 10. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Fax: (+86)22-23502458. Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS The authors thank the NSFC (21331003 and 21373115), the MOE (NCET-13-0305 and IRT13R30), and 111 Project (B12015). REFERENCES (1) Zhou, H.-C. and Kitagawa, S. Chem. Soc. Rev. 2014, 43, 5415-5418. (2) Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112, 673-674. (3) Cook, T. R.; Zheng, Y.-R. and Stang, P. J. Chem. Rev. 2013, 113, 734-777. (4) Yaghi, O. M.; O’Keeffe, M.; Ockwing, N. W.; Chae, H. K.; Eddaoudi, M. and Kim, J. Nature, 2003, 423, 705-714. (5) Furukawa, H.; Cordova, K. E.; O’Keeffe, M. and Yaghi, O. M. Science, 2013, 341, 974. (6) Suh, M. P.; Park, H. J.; Prasad, T. K. and Lim, D.-W. Chem. Rev. 2012, 112, 782-835. (7) Murray, L. J.; Dincă M. and Long, J. R. Chem. Soc. Rev. 2009, 38, 1294-1314. (8) He, Y.; Zhou, W.; Qian G. and Chen, B. Chem. Soc. Rev. 2014, 43, 5657-5678. (9) Sumida, K.; Rogow, D. L.; Mason, J. A.; McMondald, T. M.; Bloch, E.; Herm, Z. R.; Bae, T.-H. and Long, J. R. Chem. Rev. 2012, 112, 724-781. (10) Yang, Q.; Liu, D.; Zhong, C. and Li, J.-R. Chem. Rev. 2013, 113, 8261-8323. (11) Li, J.-R.; Sculley, J. and Zhou, H.-C. Chem. Rev. 2012, 112, 869-932. (12) Van de Voorde, B.; Bueken, B.; Denayer, J. and De Vos, D. Chem. Soc. Rev. 2014, 43, 5766-5788. (13) Li, J. R.; Kuppler, R. J. and Zhou, H. C. Chem. Soc. Rev. 2009, 38, 1477-1504. (14) Corma, A.; García, H.; and Llabrés I Xamena, F. X. Chem. Rev. 2010, 110, 4606-4655. (15) Yoon, M.; Srirambalaji, R. and Kim, K. Chem. Rev. 2012, 112, 1196-1231. (16) Liu, J.; Chen, L.; Cui, H.; Zhang, J.; Zhang, L. and Su, C.-Y. Chem. Soc. Rev. 2014, 43, 6011-6061. (17) Dhakshinamoorthy, A. and Garcia, H. Chem. Soc. Rev. 2014, 43, 5750-5765.


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For Table of Contents Use Only

A Series of 3d-4f Heterometallic Metal-Organic Frameworks Based on 2,2’-Bipyridine-3,3’dicarboxylic Acid: Syntheses, Structures and Magnetic Properties Ke Liu, Jing-Min Zhou, Hui-Min Li, Na Xu* and Peng Cheng*


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A series of LnIII-CuII heterometallic MOFs have been successfully synthesized, structurally and magnetically characterized. Three types of structures with interesting topologies are depending on different lanthanide ions and versatile coordination modes of the mixed-donor ligand 2,2’bipyridine-3,3’-dicarboyxlic acid.


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Different appearances of crystals for the three types of Ln-Cu MOFs. 529x327mm (96 x 96 DPI)


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Plots of χT vs T curves for complexes 1-10. 273x168mm (120 x 120 DPI)



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A Series of CuIIâLnIII MetalâOrganic Frameworks Based on 2,2

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