Construction of Designated Heptanuclear Metal 8-hydroxyquinolates

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Construction of Designated Heptanuclear Metal 8hydroxyquinolates with Different Ions and Auxiliary Co-ligands Ting Zhang, Linlin Zhang, Cuixian Ji, Shuai Ma, Yingxi Sun, Jiong-Peng Zhao, and Fu-Chen Liu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00265 • Publication Date (Web): 13 May 2019 Downloaded from http://pubs.acs.org on May 14, 2019

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Crystal Growth & Design

Construction of Designated Heptanuclear Metal 8-hydroxyquinolates with Different Ions and Auxiliary Co-ligands Ting Zhang,† Lin-Lin Zhang,† Cui-Xian Ji,† Shuai Ma,† Ying-Xi Sun,† Jiong-Peng Zhao,* † and Fu-Chen Liu*† †School

of Chemistry and Chemical Engineering, TKL of Organic Solar Cells and Photochemical Conversion, Tianjin

University of Technology, Tianjin, 300384, P. R. China. Supporting Information Placeholder ABSTRACT: A series of metal 8-hydroxyquinolates {[Ni7 (µ2-L1)6(µ3-L1)2(OAc)2(µ7-L2)(OCH3)]·CH3OH·CH3CN} (1), {[Ni7(µ2L1)6(µ3-L1)3(SCN)2(µ7-L2)(CH3CN)]·(CH3OH)2·CH3CN} (2), [Ni5Dy2(µ2-L1)6(OAc)4(µ7-L2)2] (3), [Ni6Dy(µ2-L1)6(µ3L1)2(OAc)3(µ3-L2)(OCH3)] (4), [Ni6Dy(µ2-L1)6(µ3L1)2(OAc)2(NO3)(OH)2(OCH3)2] (5) (HL1=8-hydroxyquinolne, H3L2=1,1,1-Tris(hydroxymethyl)-Ethane) have been solvothermally prepared. Those clusters feature the heptanuclear disk-like structure with 8-hydroxyquinolne as corner ligands in restricting the expansion of the triangular lattice in spite of the metal ions or auxiliary co-ligands. The magnetic properties of those comp lexes vary according to metal ions and auxiliary co-ligands, in which slow magnetic relaxation is found in 5.

Introduction The assembling of 3d and/or 4f coordination clusters (CCs) consisting atomically precise metal cores protected by a shell of capping ligands are significant in both crystal engineering and properties investigations.1 The CCs with small nuclearity are usually considered as the building block of many highnuclear clusters2-3 or coordination polymers.4-8 For example, the cubane-like cluster units could be used to construct giant molecular aggregates,9-10 and the Zr6 cluster could be linked by carboxylate ligands in producing various Zr(IV)-MOF.11 That reveals the importance of the small nuclearity CCs. Thus ， assembling such CCs with controllable structure and composition is a key point in crystal design and growth. There are several facts that can determine the final structures of these CCs, which includes the coordination geometry of the metal ions, the ligands, solvent and other synthesis conditions i.e. ,temperature, pressure and so on. Despite great deal of approaches has been applied to synthesize CCs in a more predictable manner, that is still a challenging task for researchers.12-16 It is an ideal and universal strategy to obtain zerodimensional (OD) CCs by restricting the growth of the complexes in high dimension. Restricting the augmentation of the two-dimensional (2D) structures, constructed of repeat units in two directions, may be a good method to acquire disk -like symmetrical zero-dimensional (0D) structure,17 such as the heavily reported 2D hexagonal structure,18 quadrangular structure,19,20 triangular structure.21-24 The symmetry natures of those lattices make it easy to cut down the structure into OD structure by disconnecting the same linkage of the nodes. And

by the topological analysis, the high-symmetry hexagonal 36 nets with triangle as based units is a good choice to realize disk-like finite ‘cutout’ structure (Scheme 1).25-29 Herein, the

Scheme 1. The metal core of the complexes mapped onto an ideal triangular net.

attempt of using 8-hydroxyquinolne to reduce the connections of the metal ions to restrict the expansion of the triangular lattice is taken into practice. As a result, a series of disk-like heptanuclear CCs namely, {[Ni7(µ2-L1)6(µ3-L1)2(OAc)2(µ7L2)(OCH3)]·CH3OH·CH3CN} (1), {[Ni7(µ2-L1)6(µ3L1)3(SCN)2(µ7-L2)(CH3CN)]·(CH3OH)2·CH3CN} (2), [Ni5Dy2(µ2-L1)6(OAc)4(µ7-L2)2] (3), [Ni6Dy(µ2-L1)6(µ3L1)2(OAc)3(µ3-L2)(OCH3)] (4), [Ni6Dy(µ2-L1)6(µ31 L )2(OAc)2(NO3)(OH)2(OCH3)2] (5) (HL1 = 8hydroxyquinoline, H3L2 = 1,1,1-Tris(hydroxymethyl)-Ethane)) were obtained. Despite different metal ions and auxiliary coligands used in those complexes, they all have a M7O12 core like the ‘cutout’ structure of a 36 nets. Mainly ferromagnetic

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magnetic interactions were found in between the NiII ions, and Table 1. Crystal data for 1–5. 1

2

3

4

5

Formula

C85H73N9Ni7O17

C94H77N13Ni7O14S2

C72H66Dy2N6Ni5O20

C84H69DyN8Ni6O18

C78H62DyN9Ni6O19

Mr (g mol-1)

1903.49

2087.68

1953.85

1993.23

1944.06

Space group

P-1

P21/c

P21/n

P21/c

P21/n

Crystal system a/Å

Triclinic

monoclinic

monoclinic

monoclinic

monoclinic

14.1831(11)

19.2410(9)

10.4615(12)

19.569(2)

14.4849(12)

b/Å

14.7121(10)

16.2373(7)

23.128(2)

14.6482(10)

25.1331(17)

c/Å

20.7524(13)

30.3997(17)

14.6047(17)

30.905(2)

22.008(2)

α/deg

87.979(5)

90

90

90

90

β/deg

84.176(6)

103.777(5)

91.218(10)

102.833(8)

107.871(10)

γ/deg

64.744(7)

90

90

90

90

V/Å3

3896.0(5)

9224.3(8)

3532.8(7)

8637.7(12)

7625.6(12)

Z

2

4

2

4

4

Dc (gcm-3)

1.623

1.503

1.837

1.533

1.692

μ (mm-1)

1.732

1.507

3.470

2.203

2.494

Ra

0.0748

0.0514

0.0815

0.0895

0.0603

wRb

0.2482

0.1409

0.2507

0.2836

0.1680

GOF on F2

1.002

1.059

1.044

1.003

1.048

aR =∑ 1

||Fo| - |Fc||/∑|Fo| . b wR2={∑[w(Fo2 - Fc2)2]/∑w(Fo2)2}1/2

slow magnetic relaxation was detected in DyIII involved complexes 5.

module of the Mercury (Hg) program available free of charge via the Internet at http://www.iucr.org. Thermogravimetric analyses were carried out on a TGA Q5000 (TA Instruments) under constant flow of nitrogen. The Magnetic Measurements of 1-5 are performed by an MPMS-XLSQUID magnetometer equipped with a 5 T magnet. Diamagnetic corrections are estimated by using Pascal constants and background corrections by experimental measurement on sample holders.

Experimental Section Materials and Physical characterisations. The reagents of Ni(OAc)2·4H2O (99.9%), NiSO4·6H2O (99.9%), 8-hydroxyquinoline(HL1) (99.9%), 1,1,1-Tris (hydroxymethyl)-Ethane (H3L2) (99.9%), Dy(NO3)3·6H2O (99.9%), H3BO3 (99.9%), NaHCO3 (99.9%), methyl alcohol (99.5%) and acetonitrile (99.5%) are considered standard. Elemental analyses (C, H, N) were performed on a PerkinElmer 240C elemental analyzer. IR spectra was measured on a Tensor 27 OPUS (Bruker) FT-IR spectrometer with KBr pellets. PXRD is recorded on a Rigaku D/Max-2500 diffractometer at 50kV, 40mA for a Cu-target tube, and a graphite monochromator. Simulation of the PXRD spectra is carried out by the single-crystal data and diffraction-crystal

Synthesis of {[Ni7(µ2-L1)6(µ3-L1)2(OAc)2(µ7L2)(OCH3)]·CH3OH·CH3CN} (1). Mixture of Ni(OAc)2·6H2O (0.21 mmol), HL1 (0.19 mmol), H3L2 (0.33 mmol), NaHCO3 (0.6mmol), 10 mL of acetonitrile, and 5 mL of methyl alcohol was sealed in a 25 mL Teflonlined stainless steel autoclave. The autoclave was heated at 120 °C for 72h under autogenous presser and then cooled slowly to room temperature at a rate of 2 °C h-1. Green blocky crystals were obtained. Green blocky crystals of 1 were harvested in yields of 25%. (based on HL1). Elemental

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temperature at a rate of 2 °C/h. Green blocky crystals were obtained. Green blocky crystals of 5 were harvested in yields of 25% (based on HL1). Elemental analysis calcd (%) for C78H62DyN9Ni6O19(1944.06): C, 48.19; H, 3.21; N, 6.48. Found: C, 48.50; H, 3.67; N, 6.86 %. IR/cm-1(KBr): 3043, 2805, 1577, 1500, 1468, 1425, 1382, 1325, 1112, 822, 786, 739cm-1.

analysis calcd (%) for C85H73N9Ni7O17 (1903.49): C, 53.64; H, 3.87; N, 6.62. Found: C, 53.60; H, 3.91; N, 6.68 %. IR/cm1(KBr): 3043, 2873, 1575, 1498, 1487, 1386, 1325, 1112, 1047, 823, 787, 738cm-1. (Figure S1, Supporting Information). {[Ni7(µ2-L1)6(µ3-L1)3(SCN)2(µ7L2)(CH3CN)]·(CH3OH)2 ·CH3CN} (2). 2 was synthesized with different protocol of 1 by replacing Ni(OAc)2·6H2O with NiSO4·6H2O and adding NaSCN. Mixture of NiSO4·6H2O (0.41 mmol), HL1 (0.38 mmol), H3L2 (0.33 mmol), NaSCN (0.6 mmol), NaHCO3 (0.6 mmol), 10 mL of acetonitrile, and 5 mL of methyl alcohol was sealed in a 25 mL Teflon-lined stainless steel autoclave. The autoclave was heated at 120 °C for 72h under autogenous presser and then cooled slowly to room temperature at a rate of 2 °C/h. Green flaky crystals were obtained. Green flaky crystals of 2 were harvested in yields of 25%. (based on HL1). Elemental analysis calcd (%) for C94H77N13Ni7O14S2(2087.68): C, 54.08; H, 3.72; N, 8.72. Found: C, 54.40; H, 3.65; N, 8.51 %. IR/cm1(KBr): 3033, 2874, 2094, 1577, 1499, 1466, 1380, 1324, 1112, 822, 787, 737cm-1. [Ni5Dy2(µ2-L1)6(OAc)4(µ7-L2)2] (3). 3 was synthesized with different protocol of 1 by adding Dy(NO3)3·6H2O. Mixture of Ni(OAc)2·6H2O (0.21 mmol), HL1 (0.19 mmol), Dy(NO3)3·6H2O (0.061 mmol), H3L2 (0.33 mmol), NaHCO3 (0.6 mmol),10 mL of acetonitrile, and 5 mL of methyl alcohol was sealed in a 25 mL Teflon-lined stainless steel autoclave. The autoclave was heated at 120 °C for 72h under autogenous presser and then cooled slowly to room temperature at a rate of 2 °C/h. Green flaky crystals were obtained. Green flaky crystals of 3 were harvested in yields of 27% (based on HL1). Elemental analysis calcd (%) for C72H66Dy2N6Ni5O20(1953.85): C, 44.26; H, 3.40; N, 4.30. Found: C, 44.35; H, 3.53; N, 4.56 %. IR/cm-1(KBr): 3054, 2873, 1577, 1500, 1469, 1380, 1322, 1111, 1036, 824, 787, 739, 516cm-1. [Ni6Dy(µ2-L1)6(µ3-L1)2(OAc)3(µ3-L2)(OCH3)] (4). 4 was synthesized with different protocol of 3 by reducing the concentration ratio of Ni(OAc)2·6H2O to Dy(NO3)3·6H2O. Mixture of Ni(OAc)2·6H2O (0.21 mmol), HL1 (0.38 mmol), Dy(NO3)3·6H2O (0.041 mmol), H3L2 (0.33 mmol), NaHCO3 (0.6 mmol), 10 mL of acetonitrile, and 5 mL of methyl alcohol was sealed in a 25 mL Teflon-lined stainless steel autoclave. The autoclave was heated at 120 °C for 72h under autogenous presser and then cooled slowly to room temperature at a rate of 2 °C/h. Green flaky crystals were obtained. Green flaky crystals of 4 were harvested in yields of 20% (based on HL1). Elemental analysis calcd (%) for C84H69DyN8Ni6O18 (1993.23): C, 50.62; H, 3.49; N, 5.62. Found: C, 50.42; H, 3.34; N, 5.77 %. IR/cm-1(KBr): 3054, 1582, 1501, 1464, 1384, 1327, 1117, 1054, 824, 782, 739cm-1. [Ni6Dy(µ2-L1)6(µ3-L1)2(OAc)2(NO3)(OH)2(OCH3)2] (5). 5 was synthesized with different protocol of 4 by adding H3BO3, dislodging H3L2 and acetonitrile, and reducing temperature of the reaction. Mixture of Ni(OAc)2·4H2O (0.21 mmol), HL1 (0.38 mmol), Dy(NO3)3·6H2O (0.1mmol), H3BO3 (0.39 mmol), NaHCO3 (0.3 mmol), 15 mL of methyl alcohol was sealed in a 25 mL Teflon-lined stainless steel autoclave. The autoclave was heated at 110 °C for 72h under autogenously presser and then cooled slowly to room

SCXRD Data Determinations.

Collection

and

Structure

Single crystal X-ray diffraction data of 1-5 are produced using the XtaLAB-mini diffractometer at 293(2) K with MoKα radiation (λ=0.71073Å) by ω scan mode. The experimental time and the diffraction angle range are set according to the size, type, and diffraction intensity of the single crystal, then the diffraction data is collected. The structure is solved by direct method using the SHELXT program of the SHELXTL201430 package and refined by full-matrix least-squares methods with SHELXTL-2014.31 Then, the position coordinates of non-hydrogen atoms are determined by the difference Fourier method, and the anisotropic thermal parameters are refined to convergence by F2. The hydrogen atoms of the ligands are generated theoretically onto the specific atoms and refined isotropically with fixed thermal factors. The structure factor contributions from spatially disordered solvent molecules inside the pores in 1 and 2 were taken into account using SQUEEZE.32 The CCDC numbers for 1-5 are 1899133-1899137. Detailed crystallographic data is summarized in Table 1. The phase purity is confirmed by PXRD (Figure S2-S6, Supporting Information).

Results and Discussion Description of crystal structure.

Scheme 2. Coordination modes of ligands L1 and L2.

Figure 1. (a) Disk like view of the molecular structures of 1 for that hydrogen atoms are omitted for clarity. (b) Side view of the disk structure of 1 for that carbon atoms of L1 and



by six µ3-O to form a disk-like node configuration. The pores are filled with disordered solvent molecules in the assynthesized compound. There are two CH3OH and one CH3CN solvent molecules per formula taking the solventaccessible volume, which is confirmed by elemental and thermal analysis (Figure S7, Supporting Information).

hydrogen atoms are omitted.

First, the coordination modes of L1 and L2 are summarized in (Scheme 2). The oxygen atom of L1 connects two metal ions using µ2 coordination manner or bridges with three metal ions through µ3 coordination manner, thus there are two different coordination types for L1: µ2:η2η1-L1, µ3:η3η1-L1. And the oxygen atoms from L2 are coordinated respectively with three metal ions through µ3 coordination manner, thus there is a coordination type for L2: µ7:η3η3η3-L2. 1 crystallize in the space P-1 group, and the crystallographic unit contains seven NiII ions, two acetic anions, one deprotonated methanol, six µ2-L1, two µ3-L1 and one µ7-L2. (Figure 1) The disk-like metal node consisted of a hexanuclear NiII wheel, a central NiII center, and the seven Ni ions are sixcoordinated respectively adopting distorted octahedral geometries. The equatorial positions of Ni1 are occupied by two µ2-O atoms (O1, O2) from µ2-L1, O3 from µ3-L1 and O14 from acetic anion; axial positions are occupied by N1 from µ3L1 and O9 from µ7-L2. The equatorial positions of Ni2 are occupied by N2 from µ2-L1, O5 from µ3-L1, O9 from µ7-L2 and O15 from acetic anion; axial positions are occupied by two µ2-O atoms (O4, O1) from µ2-L1. The equatorial positions of Ni3 are occupied by two µ2-O atoms and one N atom (O6, O2, N4) from µ2-L1 and O3 from µ3-L1; the axial positions are occupied by N3 from µ2-L1 and O10 from µ7-L2. The equatorial positions of Ni4 are occupied by O5 from µ3-L1, two µ3-O atoms (O9, O10) from µ7-L2 and O16 from deprotonated methanol; axial positions are occupied by O3 from µ3-L1 and O11 from µ7-L2. The equatorial positions of Ni5 are occupied by two µ2-O atoms (O4, O7) from µ2-L1, N5 from µ3-L1 and O11 from µ7-L2; axial positions are occupied by N6 from µ2-L1 and O5 from µ3-L1. The equatorial positions of Ni6 are occupied by O10 from µ7-L2, O16 from deprotonated methanol and two µ1-O atom (O13, O12) from an acetic anion; axial positions are occupied by two µ2-O atoms (O6, O8) from µ2-L1. The equatorial positions of Ni7 are occupied by two µ2-O atoms and one N atom (O7, O8, N7) from µ2-L1 and O11 from µ7-L2; axial positions are occupied by N8 from µ2-L1 and O16 from deprotonated methanol. The values of Ni-O and Ni-N bond lengths are given in Tables S1. In 1, six µ3-O atoms stem from respectively two µ3-L1, one µ7L2 and one deprotonated methanol. Three NiII ions, coordinated with one µ3-O, forming a triangular conformation, and seven NiII ions are bridged by six µ3-O in this way to form the disk-like node configuration. There are one CH3OH and one CH3CN solvent molecules per formula taking the solventaccessible volume, which is confirmed by elemental and thermal analysis (Figure S7, Supporting Information). 2 crystallize in the space P21/c group. In the crystallographic unit, there are seven NiII ions, two thiocyanate anions, an acetonitrile, six µ2-L1, three µ3-L1 and one µ7-L2 (Figure 2). The disk-like metal node is similar to 1, composing of a hexanuclear NiII wheel and a central NiII center. Seven Ni ions are six-coordinated respectively adopting distorted octahedral geometries, and the details will not be described. The values of Ni-O and Ni-N bond lengths are given in Tables S2. In 2, six µ3-O atoms stem from three µ3-L1 ligands and one µ7-L2. Likewise, three NiII ions, coordinated with one µ3-O, form a triangular conformation, and seven NiII ions are bridged

Figure 2. (a) Disk like view of the molecular structures of 2 for that hydrogen atoms are omitted for clarity. (b) Side view of the disk structure of 2 for that carbon atoms of L1 and hydrogen atoms are omitted.


3 crystallize in the space P21/n group. The crystallographic unit contains five NiII ions, two DyIII ions, four acetic anions, six µ2-L1 and two µ7-L2, and the molecule has centrosymmetric site symmetry in the crystal (Figure 3). Dy1 is coordinated by the seven-coordinated method with seven oxygen atoms, two µ2-O atoms (O1, O21) from µ2-L1, two µ3O atoms (O51, O6) from µ7-L2 and three µ1-O atoms (O8, O9, O10) from two acetic anions. The Dy1-O bond distances are in the range of 2.210(10)-2.450(14) Å. Five Ni ions are sixcoordinated adopting distorted octahedral geometries, and the details will not be described. The values of Ni-O and Ni-N bond lengths are given in Tables S3. In 3, three metal ions, coordinated with one µ3-O, form a triangular conformation, and five NiII and two DyIII ions are bridged by six µ3-O in this way to form a disk-like node configuration.


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4 crystallize in the space P21/c group. In the crystallographic asymmetric unit, there are six NiII ions, one DyIII ion, three acetic anions, one deprotonated methanol, six µ2-L1, two µ3-L1 and one µ7-L2 (Figure 4). The Dy1 is located in the hexanuclear wheel of disk-like structure, and the geometry of DyIII can be described as transmutative double-capped triangular prism constructed by eight oxygen atoms. Eight oxygen atoms derive from two µ2-L1 ligands, one µ7-L2 ligand, two acetic anions, and one deprotonated methanol. The Dy1-O bond distances are in the range of 2.237(10)-2.56(2) Å. Six Ni ions are six-coordinated adopting distorted octahedral geometries, and the details will not be detailed. The values of Ni-O and Ni-N bond lengths are given in Tables S4. In 4, six µ3-O atoms are from respectively two µ3-L1, one µ7-L2 and one deprotonated methanol. And six NiII and one DyIII ions are bridged by six µ3-O to form a disk-like node configuration.

5 crystallize in the space P21/n group. The crystallographic unit contains six NiII ions, one DyIII ion, two acetic anions, one nitrate anion, two deprotonated methanols, two hydroxyls, six µ2-L1 and two µ3-L1(Figure 5). Dy1 is located in the hexanuclear wheel of disk-like structure, and coordinated with eight oxygen atoms using an eight-coordinated method. Eight oxygen atoms derive from two µ2-L1, one nitrate anion, two acetic anions, and two deprotonated hydrones. The Dy1-O bond distances are in the range of 2.260(6)-2.494(7) Å. Six Ni ions are six-coordinated respectively adopting distorted octahedral geometries, and the details will not be detailed. The values of Ni-O and Ni-N bond lengths are given in Tables S5. In 5, six µ3-O atoms are respectively from two µ3-L1, two hydroxyls and two deprotonated methanols. And six NiII and one DyIII ions are bridged by six µ3-O to form a disk-like node configuration. The structures of the disk like M7O12 core of 15 are shown in Figure 6 that reveals the disk-like structure conformation do not change in the variation of metal ions and auxiliary co-ligands. And it is worth that the syn,syn acetate and µ2-L1 bridged Ni2 or DyNi unit were found in the complexes 1,3,4,5 with acetate as Ni(OAc)2·4H2O as reagents that indicated the syn,syn acetate and µ2-8-hydroxyquinolate co-bridged dinuclear units are easy to form and could be a stable subunit in assembling. In the synthesis of the five complexes some reagents such as NaHCO3/ H3BO3 were used as mineralizers, the anions do not participate the coordination to the metal ions and just adjust the pH value.

Magnetism Studies


The magnetic susceptibility data collected on crystalline samples of these CCs in the 2-300K temperature range is shown in Figure 7(a-b), in which the date of 1-5 are under 1kOe. The χmT vs T behaviours are different of these CCs. The χmT products of the 1-2 increase on cooling until reaching a maximum at 7K, then drop rapidly33. The behavior of the χmT products increases sustaining on cooling, indicating ferromagnetic coupling between the ions. The experimental data of 1 and 2 for χm versus T in the specific range is fitted according to the Curie-Weiss law (Figure S8 (a), Supporting Information), which give C = 12.05cm3Kmol-1, θ = 8.65K for 1 and C = 7.78cm3Kmol-1, θ = 9.16K for 2. The positive Weiss constant also indicates the presence of ferromagnetic interaction. As the temperature decreased, the χmT products of 4 increases smoothly between 300-50K and increases sharply to a maximum of 33.49cm3Kmol-1 at 2K. Different from 4, the χmT products of the 3 reduce steadily on cooling until reaching a minimum at 46K then increase sharply on further cooling. Similar with 3, during the cooling process, the χmT products of the 5 show almost no change over a wide temperature range of 300-100K, then drop and reach a value of 21.51cm3Kmol-1 at 26K, then increase to 23.43cm3Kmol-1 at 7K, and they begin to drop sharply again on further cooling. The decline of χmT below 7K is on account of saturation. The experimental data of 3, 4 and 5 for χm versus T in the specific range is fitted according to the Curie-Weiss law (Figure S8 (b), Supporting Information), which give C = 41.46 cm3Kmol-1, θ = -13.13K for 3; C = 19 cm3Kmol-1, θ = 10.86K for 4; C = 23.46 cm3Kmol-1, θ = -2.52 K for 5. The field-dependent measurements of magnetization and the hysteresis loop are performed at 2K for 1-5, which are shown in Figure 7(c-d).


Figure 6. From left to right are the structures of the disk-like M7O12 core of the complexes 1-5 respectively.



The magnetization of 1-5 have sharply increasing at low field. The value of the magnetization of 1 and 4 at 5T reach 12.96 Nβ and 16.58 Nβ, which are near the saturation values. In 3 the magnetization reaches saturation and gives a value 22.34 Nβ. However in 2 and 5 that give the value of 11.07 Nβ and 12.84 Nβ far from saturation. The unsaturation of the magnetization of 5 suggests the presence of significant anisotropy and/or low-lying excited states.

geometry and no slow magnetic relaxation is detected.

Conclusion In summary, an ideal strategy was proposed to assemble new CCs by restricting the growth of low or high dimensional structure. On the basis of a disk-like finite ‘cutout’ of the 2D triangular lattice, composed of six triangular configurations, a series of heptanuclear clusters Ni7, Ni5Dy2, Ni6Dy with the disk-like metal node are synthesized with various metal ions and auxiliary Co-ligands. This work provides a good and universal way to design and assemble CCs with excepted structures. In addition, magnetic studies of 1-5 indicate that the slow magnetic relaxation exists in 5.

ASSOCIATED CONTENT Supporting Information ： X-ray crystallographic data file in CIF format for 1-5, FTIR spectras (Figures S1), PXRD characterizations (Figures S2-S6), Thermogravimetry (Figures S7), Curie-Weiss plots (Figures S8) and selected bond distances (Table S1-S5).

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]; [email protected].

Figure 7. (a) Thermal variations of χmT of 1(-■-) and 2 (-■-) at 1000Oe. (b) Thermal variations of χmT of 3(-■-), 4 (-■-) and 5 (■-) at 1000Oe. (c) Plots of reduced magnetization of 1(-■-) and 2 (-■-) at 2.0K. (d) The magnetic hysteresis loop of 3(-■-), 4 (-■-) and 5 (-■-) at 2.0K.

ORCID Jiong-Peng Zhao: 0000-0003-1512-0171 Fu-Chen Liu: 0000-0001-9709-0556

Notes The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS This work was supported by the NSFC of China (21571139 and 21871209), the Natural Science Foundation of Tianjin (17JCQNJC05900) and Special Program of talents Development for Excellent Youth Scholars in Tianjin TJTZJH-QNBJRC-2-3.

REFERENCES

Figure 8. (a) Ac plot for 5 between 2K and 10K at different frequencies. (b) Magnetization relaxation time (τ) vs T-1 for 5 (solid line represents the best fit to the Arrhenius law).

(1) Beatriz, S. G.; Angelo, M.; Chiara, C.; Mirko, P.; Carlo, S.; Francesco, M.; Sergio, B. Bottom-up Synthesis and Self-Assembly of Copper Clusters into Permanent Excimer Supramolecular Nanostructures. Angew. Chem. Int. Ed. 2018, 57, 7051-7055. (2) Zhao, C. W.; Han, Y. Z.; Dai, S. Q.; Chen, X. M.; Yan, J. Z.; Zhang, W. J.; Su, H. F.; Lin, S. C.; Tang, Z. C.; Teo, B. K.; Zheng, N. F. Microporous Cyclic Titanium-Oxo Clusters with Labile Surface Ligands. Angew. Chem. Int. Ed. 2017, 56, 16252-16256. (3) Gu, Y. N.; Chen, Y.; Wu, Y. L.; Zheng, X. T.; Li, X. X. A Series of Banana-Shaped 3d-4f Heterometallic Cluster Substituted Polyoxometalates: Syntheses, Crystal Structures, and Magnetic Properties. Inorg. Chem. 2018, 57, 5, 2472-2479. (4) Wang, B.; Yang, Q.; Guo, C.; Sun, Y. X.; Xie, L. H.; Li, J. R. Stable Zr(IV)-Based Metal-Organic Frameworks with Predesigned Functionalized Ligands for Highly Selective Detection of Fe(III) Ions in Water. ACS Appl.Mater. Interfaces. 2017, 9, 10286-10295. (5) Pang, J. D.; Yuan, S.; Qin, J. S.; Wu, M. Y.; Lollar, C. T.; Li, J. L.; Huang, N.; Li, B.; Zhang, P.; Zhou, H. C. Enhancing PoreEnvironment Complexity Using a Trapezoidal Linker: Toward Stepwise Assembly of Multivariate Quinary Metal-Organic Frameworks. J. Am. Chem. Soc. 2018, 140, 12328-12332. (6) Peng, L.; Asgari, M.; Mieville, P.; Schouwink, P.; Bulut, S.; Sun, D. T.; Zhou, Z. R.; Pattison, P.; Beek, W. V.; Queen, W. L.

Ac dynamic susceptibility measurements of 1-5 were collected at low temperature, however, only 5 showed a clear out-of-phase (χm") signals. The out-of-phase (χm") signals of 5 shows frequency dependent peaks in zero static field (Figure 8a) in 10-960 Hz, indicating the presence of slow magnetic relaxation. 34,35 With increasing the ac frequency, the peaks gradually move to the high temperature region. The peak of χm" from these data can be fitted well by the Arrhenius plot giving the characteristic relaxation time (Figure 8b), corresponding energy barriers, τ0 =7.64×10-13s, Ea/kB =122.73K. And upon further cooling, the upturns of χm" are observed at lower temperatures, indicating the system is influenced by the quantum tunneling effect. The origin of that slows magnetic relaxation in 5 should be originated from the DyIII ions in a compress square-antiprismatic coordination polyhedron geometry.36,37 While in 4 the DyIII ions locates in a elongated square-antiprismatic coordination polyhedron


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Using Predefined M3(μ3-O) Clusters as Building Blocks for an Isostructural Series of Metal-Organic Frameworks. ACS Appl. Mater. Interfaces. 2017, 9, 23957-23966. (7) Hu, H. C.; Cui, P.; Hu, H. S.; Cheng, P.; Li, J.; Zhao, B. Stable ZnI-Containing MOFs with Large [Zn70] Nanocages from Assembly of ZnII Ions and Aromatic [ZnI 8 ] Clusters. Chem. Eur. J. 2018, 24, 3683-3688. (8) Dhers, S.; Feltham, H. L. C.; Rouzières, M.; Cléracb, R.; Brooker, S. Macrocyclic {3d-4f} SMMs as Building Blocks for 1Dpolymers: Selective Bridging of 4f ions by Use of an O-donor Ligand. Dalton Trans. 2016, 45, 18089-18093. (9) Peng, J.-B.; Zhang, Q.-C.; Kong, X.-J.; Zheng, Y.-Z.; Ren, Y.P.; Long, L.-S.; Huang, R.-B.; Zheng, L-S.; Zheng, Z. HighNuclearity 3d-4f Clusters as Enhanced Magnetic Coolers and Molecular Magnets. J. Am. Chem. Soc. 2012, 134, 3314-3317. (10) Han, X.-B.; Li, Y.-G.; Zhang, Z.-M.; Tan, H.-Q.; Lu, Y.; Wang, E.-B. Polyoxometalate-Based Nickel Clusters as Visible LightDriven Water Oxidation Catalysts. J. Am. Chem. Soc. 2015, 137, 5486-5493. (11) (a) Bai, Y.; Dou, Y.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-C. Zr-Based Metal-Organic Frameworks: Design, Synthesis, Structure, and Applications. Chem. Soc. Rev. 2016, 45, 2327-2367. (b) Wang, B.; Lv, X.-L.; Feng, D.; Xie, L.-H.; Zhang, J.; Li, M.; Xie, Y.; Li, J.-R.; Zhou, H.-C. Highly Stable Zr(IV)-Based Metal-Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water. J. Am. Chem. Soc. 2016, 138, 62046216. (12) Omid, S.; Mehran, A.; Eric W, R.; May, N. The Role of Bi3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid. Angew. Chem. Int. Ed. 2018, 57, 6247-6250. (13) Wu, J.; Zhao, L.; Zhang, L.; Li, X. L.; Guo, M.; Powell, A. K.; Tang, J. Macroscopic Hexagonal Tubes of 3d-4f Metallocycles. Angew. Chem. Int. Ed. 2016, 55, 15574-15578. (14) Zou, H. H.; Sheng, L. B.; Liang, F. P.; Chen, Z. L.; Zhang, Y. Q. Experimental and Theoretical Investigation of Four 3d-4f Butterfly Single-Molecule Magnets. Dalton Trans. 2015, 23, 1-23. (15) Schmitz, S.; Leusen, J. V.; Izarova, N. V.; Lan, Y.; Wernsdorfer, W.; Kögerler, Paul.; Monakhov, K. Y. Supramolecular 3d-4f Single-Molecule Magnet Architecture. Dalton Trans. 2016, 45, 16148-16152. (16) Li, C.; Li, H. D.; Xie, J.; Yang, M.; Wang, X. F.; Li, L. C. {[Ln(hfac)3]2[Cu(hfac)2]3(NIT-Pyrim)2(H2O)2} (LnIII=Gd, Ho, Er): Unique Nitronyl Nitroxide Bridged 3d-4f Heterometallic Clusters. Eur. J. Inorg. Chem. 2018, 525-530. (17) Cai,G. H.; Wang, J. P.; Wu, X. Q.; Zhan, Y. Y.; Liang, S. J. Scalable One-pot Synthesis of Porous 0D/2D C3N4 Nanocomposites for Efficient Visible-light Driven Photocatalytic Hydrogen Evolution. Appl. Surf. Sci. 2018, 459, 224-232. (18) Tu, Z. X.; Guday, G.; Adeli, M.; Haag, R. Multivalent Interactions between 2D Nanomaterials and Biointerfaces. Adv. Mater. 2018, 30, 1706709. (19) Zhuang, H. L.; Singh, A. K.; Hennig, R. G. Computational Discovery of Single-layer III-V Materials. Phys. Rev. B. 2013, 87, 165415. (20) Tong, C. J. H.; Zhang, H.; Zhang, Y. N.; Liu, H.; Liu, L. M. New Manifold Two-dimensional Single-layer Structures of Zincblende Compounds. J. Mater. Chem. A. 2014, 2, 17971-17978. (21) Lau, K. C.; Pandey, R. Stability and Electronic Properties of Atomistically-Engineered 2D Boron Sheets. J. Phys. Chem. C. 2007, 111, 7, 2906-2912. (22) Boustani, I. Systematic Ab Initio Investigation of Bare Boron Clusters: mDetermination of the Geometry and Electronic Structures of Bn (n=2-14). Phys. Rev. B. 1997, 55, 16426. (23) Chacko, S.; Kanhere, D. G.; Boustani, I. Ab initio density functional investigation of B24 clusters: Rings, tubes, planes, and cages. Phys. Rev. B. 2003, 68, 035414. (24) Boustani, I.; Rubio, A.; Alonso, J. A. Ab Initio Study of B32 Clusters: Competition Between Spherical, Quasiplanar and Tubular

Isomers. Chem. Phys. Lett. 1999, 311, 21-28. (25) Li, L. J.; Ali, B.; Chen, Z.; Sun, Z. M. Recent Advances in Aromatic Antimony Clusters. Chin. J. Chem. 2018, 36, 955-960. (26) Caia, D.; Hanb, A.; Yanga, P. Y.; Wua , Y. F.; Dub, P.; Kurmooc , M.; Zenga, M. H. Heptanuclear Co, Ni and Mixed Co-Ni Clusters as High-performance Water Oxidation Electrocatalysts. Electrochim. Acta. 2017, 249, 343-352. (27) Griffiths, K.; Harding, C.; Dokorou, V. N.; Loukopoulos, E.; Sampani, S. I.; Abdul-Sada, A.; Tizzard, G. J.; Coles, S. J.; Lorusso, G.; Evangelisti, M.; Escuer, A.; Kostakis, G. E. Heptanuclear DiskLike MII3LnIII4 (M=Ni, Co) Coordination Clusters: Synthesis, Structures and Magnetic Properties. Eur. J. Inorg. Chem. 2017, 39383945. (28) Sharples, J. W.; Collison, D.; McInnes, E. J. L.; Schnack, J.; Palacios, E.; Evangelisti, M. Quantum Signatures of a Molecular Nanomagnet in Direct Magnetocaloric Measurements. Nat. Commun. 2014, 5, 5321-5326. (29) Zhang, Y.-Z.; Wernsdorfer, W.; Pan, F.; Wang, Z.-M.; Gao, S. An azido-bridged disc-like heptanuclear cobalt(II) cluster: towards a single-molecule magnet. Chem. Commun., 2006, 3302–3304. (30) Sheldrick, G. M. SHELXT-Integrated space-group and crystal-structure determination. Acta Crystallogr., Sect. A: Found. Adv. 2015, 71, 3-8. (31) Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3-8. (32) Spek, A. Structure validation in chemical crystallography. Acta Crystallogr., Sect. D: Biol. Crystallogr. 2009, 65, 148-155. (33) Richardson, P.; Alexandropoulos, D. I.; Cunha-Silva, L.; Lorusso, G.; Evangelisti, M.; Tang, J. K.; Stamatatos, T. C. ‘All Three-in-one’: Ferromagnetic Interactions, Single-molecule Magnetism and Magnetocaloric Properties in a New Family of [Cu4Ln] (LnIII = Gd, Tb, Dy) Clusters. Inorg. Chem. Front. 2015, 2, 945-948. (34) Wu, S. Q.; Miyazaki, Y. J.; Nakano, M.; Su, S. Q.; Yao, Z. S.; Kou, H. Z.; Sato, O. Slow Magnetic Relaxation in a Mononuclear Ruthenium (III) Complex. Chem. Eur. J. 2017, 23, 10028-10033. (35) Yin, D. D.; Chen, Q.; Meng, Y. S.; Sun, H. L.; Zhang, Y. Q.; Gao, S. Slow Magnetic Relaxation in a Novel Carboxylate/oxalate/hydroxyl Bridged Dysprosium Layer. Chem. Sci. 2015, 6, 3095-3101. (36) Jiang, S. D.; Wang, B. W.; Su, G.; Wang, Z. M.; Gao, S. A Mononuclear Dysprosium Complex Featuring Single-Molecule Magnet Behavior. Angew. Chem. Int. Ed. 2010, 49, 7448-7451. (37) Rinehart, J. D.; Long, J. R. Exploiting Single-ion Anisotropy in the Design of f-element Single-molecule Magnets. Chem. Sci. 2011, 2, 2078-2085.



潮潮潮潮´ Construction of Designated Heptanuclear Metal 8-hydroxyquinolates with Different Ions and Auxiliary Co-ligands Ting Zhang, Lin-Lin Zhang, Cui-Xian Ji, Shuai Ma, Ying-Xi Sun, Jiong-Peng Zhao,* and Fu-Chen Liu

On the basis of a disk-like finite ‘cutout’ of the 2D triangular lattice, composing of six triangular configurations, a series of heptanuclear coordination clusters (1-5) with disk-like M7O12 core were synthesized with various metal ions and auxiliary Co-ligands. Magnetic studies of these coordination clusters indicated that slow magnetic relaxation exists in 5.


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Construction of Designated Heptanuclear Metal 8-hydroxyquinolates

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