Exploring the Performance Improvement of magnetocaloric effect

Subscriber access provided by Saint Louis University Libraries

Communication

Exploring the Performance Improvement of magnetocaloric effect based Gd-exclusive cluster Gd60 Xi-Ming Luo, Zhao-Bo Hu, Qing-fang Lin, Weiwei Cheng, JiaPeng Cao, Chen-Hui Cui, Hua Mei, You Song, and Yan Xu J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b07841 • Publication Date (Web): 23 Aug 2018 Downloaded from http://pubs.acs.org on August 24, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 5 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

Journal of the American Chemical Society

Exploring the Performance Improvement of magnetocaloric effect based Gd-exclusive cluster Gd60 Xi-Ming Luo, †, ‡ Zhao-Bo Hu, §, ‡ Qing-fang Lin, † Weiwei Cheng, † Jia-Peng Cao, † Chen-Hui Cui, † Hua Mei,† You Song, *§ and Yan Xu *†, § †College

of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, P. R. China. §Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China

Supporting Information Placeholder ABSTRACT: Despite wide potential applications of Gd-clusters in magnetocaloric effect (MCE) owing to f7 electron configuration of Gd(III), the structural improvement in order to enhance MCE remains difficult. A new approach of the situ hydrolysis of acetonitrile is reported, and the slow release of small ligand CH3COO- is realized in the design and synthesis of high-nuclearity lanthanide clusters. A large lanthanide-exclusive cluster complex, [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96(H2O)56](NO3)15-Br1 2(dmp)5·30CH3OH·20Hdmp (1-Gd60), was isolated under solvothermal conditions. To the best our knowledge, cluster 1 possesses the high metal/ligand ratio (magnetic density) and the largest magnetic entropy change (-∆Smmax = 48.0 J kg-1 K-1 at 2 K for ΔH = 7 T) among previously reported high-nuclearity lanthanide clusters.

In order to get a better magnetocaloric effect, we focus more on the Gd(III)-exclusive objects.3,4 How to obtain products featuring novel intriguing structures and huge magnetocaloric effects seems to be the key to research.3 It is widely believed that some structure–property correlations exist in these nanoscale molecular materials.3,4 For example, for the most part, substances with high magnetic density and weak magnetic interactions have good MCE.3,6 In particular, it is an anticipated feasible scheme that the synthesis of complexes featuring a large metal/ligand mass ratio (NGd/MW) leads to a high magnetic density.3,6,8 In the reported Gd(III) cluster compounds, Gd104 is the most successful example supporting this strategy.6f The Gd104 has the highest metal/ligand mass ratio and displaying a largest -ΔSmmax value (46.9 J kg-1 K-1) among all known lanthanide clusters.6f There exists the reported smallest and simplest carboxylate (CH3COO-) in the exquisite structure, and Gd104 represents that the employment of acetate almost culminated.3,4,6f

The magnetocaloric effect (MCE) is a class of phenomenon that a reversible temperature change occurs, when some materials exposed to a changing magnetic field.1 This magnetic refrigeration technology can achieve effective cooling in more energy-efficient and environmentally friendly conditions.2 Compared with the present refrigeration technology, magnetic refrigeration has been heralded by academia and industry as a core technology of next-generation cooling method.3 The Gd(III) with f7 electron configuration possesses isotropic electron orbit, a high-spin ground state, negligible magnetic anisotropy, allowing to obtain giant MCE.4 So high-nuclearity Gd(III) clusters have been attracting significant attention due to both their potential cooling industrial applications derived from intrinsic great MCE, and aesthetically pleasing discrete structures.4,5 The substantial body of progress has been made in efforts to design and construct the high-nuclearity lanthanide cluster materials with giant MCE, including Gd(III)-exclusive and heterometallic transition metal-Gd(III) clusters,4,5 such as Gd24,6a Gd27,6b Gd36,6c Gd37,6d Gd38,6e Gd48,6e Gd104,6f Gd140,6g Ni12Gd36,7a Co10Gd42,7b Ni10Gd42,7b Ni54Gd54,7c Ni56Gd52,7d Ni64Gd78,7f Ni64Gd96.7g However, owing to strong magnetic couplings between the transition metal(3d) ions, 3d-Gd(III) aggregations own less MCE than Gd(III)-exclusive clusters.3

With reference to compounds previously reported, there existed a whole train of unique 48-metal structures (Figure S3),6e,7a,9 such as, Gd48,6e Ho48,9a Er48,9b Gd36Ni12.7a We found such an interesting phenomenon that four compounds all exhibit an extremely similar 48-metal skeletal structure with disparate organic ligands used to stabilize the clusters (Figure S3) in the above nanosized aggregations. This suggests that the original organic molecules could be replaced with smaller organic units, without the transformation of the metal skeletons. The resulting clusters may possess a high metal/ligand mass ratio and magnetic density, leading to the good MCE.3 Attempting at further obtaining clusters featuring high MCE, we explored how to introduce acetic acid into the classical clusters. Herein, we report a unique cluster 1-Gd60, w i t h t h e f o r m u l a [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96(H2O)56](NO3)15Br1 2 (dmp) 5 ·30CH 3 OH·20Hdmp (Hdmp = 2,2-dimethylol propionic acid), through Hdmp to control the hydrolysis of lanthanide metal Gd(III) ions under solvothermal conditions (See the SI). The small and simple carboxylate ligand CH3COO- was successfully anchored around the cluster through the situ hydrolysis of acetonitrile (Figure 1 and Scheme S1). Surprisingly, 1 possesses the high NGd/MW

ACS Paragon Plus Environment

Journal of the American Chemical Society 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

among lanthanide clusters, endowing it with expected colossal magnetic density.3 Investigation of the magnetic properties reveals cluster 1 exhibits the largest -ΔSmmax (48.0 J kg-1 K-1 at 2 K for ΔH = 7 T) in the Gd(III)-clusters family.3,6f The colorless octahedral crystal of 60-metal cluster was isolated via reaction of Gd(NO3)3, Hdmp, triethanolamine (H3TEOA), KBr in a mixture of methanol, acetonitrile and deionized water under solvothermal conditions (see detailed synthesis and discussion in SI). In the synthesis process, 1-Gd60 features high yield (50-60 %) and good reproducibility, which is beneficial to the characterization of materials, and the exploration of more useful properties can also be facilitated. In particular, while directly adding acetic acid-containing salts had proven to be futile for creating materials in this context, the organic ligand CH3COO- in the cluster is believed to be from in the situ hydrolysis of acetonitrile,10 which also provides a new pathway to gain clusters with high NGd/MW. Single-crystal X-ray diffraction (SCXRD) manifests 1-Gd60 crystallizes in the tetragonal crystal system, I4/m space group and consists of one cationic 60-metal nanosphere of [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96(H2O)56]32+, 12 Br-, 15 NO3- anions, 5 dmp- anions, and guest molecules (methanol and Hdmp). Due to disorder and high symmetry, the counterions and guest molecules are confirmed by SCXRD, elemental analysis, TGA, IR, and charge balance (see SI).5-7 The cationic [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96(H2O)56]32+ can be regarded as a spherical (Figure 1a) or square (Figure 1b) metal core of [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96]32+ (1a) and protected and stabilized by 56 terminal aqua ligands and CH3COO- ions. Structurally, the high-symmetry gadolinium(III) polyhedra show approximate symmetry Oh.11

Figure 1. (a) Ball-and-stick view of 60-metal core [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96]32+ (1a) of nanosphere, (b) Sticks view of 1a along the c-axis. For clarity, hydrogen atoms in hydroxide group, terminal aqua ligands and free molecules (H2O, CH3CN, CH3OH) were omitted. Color code: green, Gd; red, O; black, C. In order to facilitate the description and understanding of the structural skeleton, we consider that the core (1a) can be viewed as being built by two basic units, a triangular [Gd3(CH3COO)(μ3-OH)4]4+ (Gd3) unit (Figure 2a), and a square [Gd4(μ3-OH)8]4+ (Gd4) unit (Figure 2b). In a couple of interesting units, Gd(III) ions all occupy the vertex of triangle or square, and [Gd4(μ3-OH)8]4+ shows a cross-section of dimensions 3.9 × 3.9 Å2. Four groups of Gd3 and Gd4 units are alternately linked together through μ2-OH- and μ3-OHbridging anions, forming the square wheel subunit [Gd28(CH3COO)4(μ2-OH)8(μ3-OH)56]16+ (Gd28) (Figure 2c-d). The size of Gd28 is 17.5 × 17.5 × 4.0 Å3. Three such unique Gd28 ring structures are intersect vertically with each other by sharing 6 Gd4 units, constituting the main structure 60-metal

core [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96]32+ (Figure 2e and S4).

Page 2 of 5 (1a)

Figure 2. (a) Ball-and-stick view of triangular [Gd3(CH3COO)(μ3-OH)4]4+ unit (Gd3), (b) square [Gd4(μ3-OH)8]4+ unit (Gd4), (c) and (d) 28-metal [Gd28(CH3COO)4(μ2-OH)8(μ3-OH)56]16+ subunit (Gd28), (e) 60-metal [Gd60(CO3)8(CH3COO)12(μ2-OH)24(μ3-OH)96]32+ cationic core (1a). Color code: green/pink, Gd; red, O; black, C. Alternatively, due to high-symmetry, 1a can be divided into eight identical parts, as shown in Figure S5a. Each motif [Gd12(CO3)(CH3COO)3(μ2-OH)3(μ3-OH)24]16+ (Gd12) is made up of 12 Gd(III) ions, 3 CH3COO- ions, a CO32- ion, 3 μ2-OH- and several μ3-OH- ions (Figure S6). Gd12 has three unique Gd(III) ions, and the other Gd(III) ions are shared with adjacent segments (Figure S5b). A hexatomic ring-like structure [Gd6(CO3)(μ3-OH)12]4+ is situated in the middle of Gd12, tem-plated by CO32- (μ6: η2:η2:η2 fashion) (Figure S5c and Figure S7).10a,12 The template effect of the CO32- anions is conspicuous in the skeleton and the anions may come from the situ decomposition of ligands.6-7 Meanwhile, we define the preferred location of three Br- ions (Figure S8) as template in valid cavity of ca. 11 Å in diameter (Figure S9) though SCXRD. Not long ago, a similar {Gd60}11 cage has been reported by Zheng, and a {Er60}12 cluster has been isolated by Long in 2009. On account of different organic supporting ligands (Figure S10), there are huge discrepancies between their overall structures, which mainly manifested in the much higher symmetry of nanosphere for 1a because CH3COOsuccessfully replaced the large organic ligands (Figure 3a). Unexpectedly, some large ligands are replaced by μ2-OH(Figure S6), allowing the number of organic ligands to be effectively reduced (Figure 3). Due to effect of these factors, the 1-Gd60 cluster possesses a large NGd/MW. So, the cluster has a high magnetic density, suggesting that 1-Gd60 may exhibit a great MCE. Temperature-dependent magnetic susceptibility (χMT-T) of 1 was performed from 1.8 to 300 K in 1.0 kOe direct current (dc) field (Figure S15). The χMT value at 300 K for 1 was 480.3 cm3 K mol-1. The value is slightly big than 472.5 for the 60 high spin Gd(III) with S = 7/2, g = 2.6 The χMT value gradually decreases and reaches 162.8 cm3 K mol-1 at 1.8 K, indicating that antiferromagnetic interactions are present. Fitting the curve of χM-1 versus T with the Curie-Weiss Law (Figure S16) gives parameters C = 485.05 cm3 K mol-1 and θ = -3.71 K, showing the presence of weak antiferromagnetic interaction.6f The isothermal field-dependent magnetization (M-H) of 1 was measured at low temperature (1.8-10 K) (Figure S17). At 1.8 K, the magnetization increases slowly with the dc field increase and reaches 404 NμB at 7 T, which is slightly smaller than the calculated value 420 NμB for 1. It also indicates the

ACS Paragon Plus Environment

Page 3 of 5 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

Journal of the American Chemical Society

Figure 3. The distribution of different organic supporting ligands in 1a (a), {Er60}12 (b), {Gd60}11 (c). intramolecular antiferromagnetic interaction in 1 is very weak, so the spins are easily magnetized. Complex 1 is a paramagnet with high magnetic density and very weak magnetic interaction between ions, thus, it should possess considerable potential for magnetic refrigerants. It urges us to investigate its magnetocaloric effect. The magnetic entropy changes ∆Sm were evaluated based on the Maxwell ralation (∆Sm(T) = ∫[∂M(T, H)/∂T ]H dH).13,14 As shown in Figure 4, -∆Smmax is 48.0 J kg-1 K-1 at 2.0 K at 7 T, which is the largest among previously known lanthanide-exclusive cluster complexes (Table 1).6 The -∆Smmax value is slightly small than the theoretical limiting value of -∆Sm (52.2 J kg-1 K-1) for 1 calculated by using the equation of -∆Sm = nRln(2S+1).5,6 The difference is probably due to the weak antiferromagnetic magnetic interactions between the metal centers.6 The large MCE may be attributed to the large metal/ligand mass ratio leading to high magnetic density.3

Table 1. −ΔSmmax data based on ΔH at a given temperature for some Gd(III)-exclusive clusters. −ΔSmmax

−ΔSm max

(J kg−1 K−1)

(mJ cm−3 K−1)

ΔH, T

T, K

ref

Gd24

46.1

89.9

2.5

7

6a

Gd27

41.8

120.4

2.0

7

6b

Gd36

39.7

91.3

2.5

7

6c

Gd37

38.7

100.0

2.0

7

6d

Gd38

37.9

102

1.8

7

6e

Gd48

43.6

120.7

1.8

7

6e

Gd60

48.0

133.1

2.0

7

This work

Gd104

46.9

137.2

1.8

7

6f

Gd140

38.0

51.9

2.0

7

6g

Cluster

−ΔSmmax (mJ cm−3 K−1) = −ΔSm max (J kg−1 K−1) * ρcald (g cm-3)

Figure 4. Values of -∆Sm calculated from the magnetization data for 1 at various fields (0.50-7.00 T) and temperatures (2.0-9.0 K). In addition, the strong lanthanide-oxygen (Ln-O) bonds in cluster maybe endow them excellent stability. So, water and thermal stability of 1-Gd60 also were studied in detail (Figure S19 and S20). As expected, 1-Gd60 possesses high stability over a wide pH range (2-12) and exhibits little change after high temperature (200 °C) treatment. The features are beneficial to further explore the properties of high-nuclearity lanthanide-exclusive clusters, such as catalytic, proton-conductive and optical properties.

In summary, an interesting lanthanide-exclusive nanosphere has been successfully synthesized with high yield and good repeatability under solvothermal conditions. The prepared Gd-cluster shielded by CH3COO- possesses high symmetry and large metal/ligand ratio, leading to the largest -∆Smmax (48.0 J kg-1 K-1) among previously known lanthanide-exclusive clusters. In addition, the situ hydrolysis of solvent acetonitrile provides a new idea for the introduction of acetic acid to assemble Gd-clusters with high magnetic entropy. The work enriches the high-nuclearity lanthanide-exclusive clusters portfolio. Next, we will continue to prepare Gd-cluster-based molecular magnetocaloric materials through the situ hydrolysis of acetonitrile, while exploring more applications for high-nuclearity lanthanide clusters.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Materials and methods; Synthesis of the cluster and detailed synthetic discussion; Detailed confirmation of counterions and guest molecules; Additional structural figures; Characterizations for PXRD, TGA, IR, EDX, and

ACS Paragon Plus Environment

Journal of the American Chemical Society 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

XRF; Detailed magnetic studies; Detailed discussion of water and thermal stability; X-ray crystallographic data, including Schemes S1, Tables S1−S6, and Figures S1−S121 (PDF) X-ray crystallographic data for 1 (CIF)

*E-mail: [email protected] *E-mail: [email protected]

(7) (a) Peng, J.-B.; Zhang, Q.-C.; Kong, X.-J.; Ren, Y.-P.; Long, L.-S.; Huang, R.-B.; Zheng, L.-S.; Zheng, Z. Angew. Chem., Int. Ed. 2011, 50, 10649 –10652. (b) 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. J. Am. Chem. Soc. 2012, 134, 3314−3317. (c) Kong, X.-J.; Ren, Y.-P.; Chen, W.-X.; Long, L.-S.; Zheng, Z.; Huang, R.-B.; Zheng, L.-S. Angew. Chem., Int. Ed. 2008, 47, 2398−2401. (d) Liu, D.-P.; Lin, X.-P.; Zhang, H.; Zheng, X.-Y.; Zhuang, G.-L.; Kong, X.-J.; Long, L.-S.; Zheng, L.-S. Angew. Chem., Int. Ed. 2016, 55, 4532−4536. (e) Lin, Q.-f.; Li, J.; Luo, X.-M.; Cui, C.-H.; Song, Y.; Xu, Y. Inorg. Chem. 2018, 57, 4799−4802. (f) Chen, W.-P.; Liao, P.-Q.; Yu, Y.; Zheng, Z.; Chen, X.-M.; Zheng, Y.-Z. Angew. Chem., Int. Ed. 2016, 55, 9375−9379.

Author Contributions

(8) Song, T.-Q.; Jie Dong, J.; Yang, A.-F.; Che, X.-J.; Gao, H.-L.; Cui, J.-Z.; Zhao, B. Inorg. Chem. 2018, 57, 3144−3150.

AUTHOR INFORMATION Corresponding Author

‡ Xi-Ming Luo and Zhao-Bo Hu and contributed equally.

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was supported by the Natural Science Foundation of China (Grant 21571103 and 91622115), the Major Natural Science Projects of the Jiangsu Higher Education Institution (Grant16KJA150005) and National Key R&D Program of China (2018YFA0303203).

(9) (a) Chen, L.; Guo, J.-Y.; Xu, X.; Ju, W.-W.; Zhang, D.; Zhu, D.-R.; Xu, Y. Chem. Commun. 2013, 49, 9728-9730. (b) Wu, M. Y.; Jiang, F. L.; Yuan, D. Q.; Pang, J. D.; Qian, J. J.; AL-Thabaitic, S. A.; Hong, M. C. Chem. Commun. 2014, 50, 1113-1115. (10) (a) Sołtys-Brzostek, K.; Terlecki, M.; Sokołowski, K.; Lewiń ski, J. Coord. Chem. Rev. 2017, 334, 199−231. (b) Vilar, R. Angew. Chem., Int. Ed. 2003, 42, 1460−1477. (c) Zheng, Z. Chem. Commun. 2001, 2521–2529. (11) Qin, L.; Zhou, G.-J.; Yu, Y.-Z.; Nojiri, H.; Schrö der, C.; Winpenny, R. E. P.; Zheng, Y.-Z. J. Am. Chem. Soc. 2017, 139, 16405-16411. (12) Kong, X.-J.; Wu, Y.; Long, L.-S.; Zheng, L.-S.; Zheng, Z. J. Am. Chem. Soc. 2009, 131, 6918−6919. (13) Evangelisti, M.; Candini, A.; Affronte, M.; Pasca, E.; de Jongh, L. J.; Scott, R. T. W.; Brechin, E. K. Phys. Rev. B 2009, 79, 104414-104418.

REFERENCES (1) (a) Liu, J.-L.; Chen, Y.-C.; Guo, F.-S.; Tong, M.-L. Coord. Chem. Rev. 2014, 281, 26−49. (b) Sessoli, R. Angew. Chem., Int. Ed. 2012, 51, 43−45. (2) Zheng, Y.-Z.; Zhou, G.-J.; Zheng, Z.; Winpenny, R. E. P. Chem. Soc. Rev. 2014, 43, 1462−1475.

(14) (a) Biswas, S.; Jena, H. S.; Adhikary, A.; Konar S. Inorg. Chem. 2014, 53, 3926−3928. (b) Lorusso, G.; Sharples, J. W.; Palacios, E.; Roubeau, O.; Brechin, E. K.; Sessoli, R.; Rossin, A.; Tuna, F.; McInnes, E. J. L.; Collison, D.; Evangelisti, M. Adv. Mater. 2013, 25, 4653–4656.

(3) Zheng, X.-Y.; Kong, X.-J.; Zheng, Z.-P; Long, L.-S.; Zheng, L.-S. Acc. Chem. Res. 2018, 51, 517-525. (4) (a) Kong, X.-J.; Long, L.-S.; Zheng, Z.; Huang, R.-B.; Zheng, L.-S. Acc. Chem. Res. 2010, 43, 201−209. (b) Papatriantafyllopoulou, C.; Moushi, E. E.; Christou, G.; Tasiopoulos, A. J. Chem. Soc. Rev. 2016, 45, 1597−1628. (c) Zheng, X.-Y.; Xie, Y.; Kong, X.-J.; Long, L.-S.; Zheng, L.-S. Coord. Chem. Rev. 2017, DOI: 10.1016/j.ccr. 2017.10.023. (d) Zheng, Y.-Z.; Zheng, Z.; Chen, X.-M. Coord. Chem. Rev. 2014, 258, 1−15. (e) Dong, J.; Cui, P.; Shi, P.-F.; Cheng, P.; Zhao, B. J. Am. Chem. Soc. 2015, 137, 15988−15991. (f) Lorusso, G.; Sharples, J. W.; Palacios, E.; Roubeau, O.; Brechin, E. K.; Sessoli, R.; Rossin, A.; Tuna, F.; Mclnnes, E. J. L.; Collison, D.; Evangelisti, M. Adv. Mater. 2013, 25, 4653−4656. (g) Qin, L.; Yu, Y.-Z.; Liao, P.-Q.; Xue, W.; Zheng, Z.; Chen, X.-M.; Zheng, Y.-Z. Adv. Mater. 2016, 28, 10772−10779. (5) (a) Zheng, X.-Y.; Zhang, H.; Wang, Z.; Liu, P.; Du, M.-H.; Han, Y.-Z.; Wei, R.-J.; Ouyang, Z.-W.; Kong, X.-J.; Zhuang, G.-L.; Long, L.-S.; Zheng, L.-S. Angew. Chem., Int. Ed. 2017, 56, 11475-11479. (b) Lin, Q.; Li, J.; Dong, Y.; Zhou, G.; Song, Y.; Xu, Y. Dalton Trans. 2017, 46, 9745–9749. (c) Lin, Q.; Zhang, Y. Cheng, W.; Liu, Y.; Xu, Y. Dalton Trans. 2017, 46, 643–646. (d) Zhang, Z.-M.; Pan, L.-Y.; Lin, W.-Q.; Leng, J.-D.; Guo, F.-S.; Chen, Y.-C.; Liu, J.-L.; Tong, M.-L. Chem. Commun. 2013, 49, 8081−8083. (6) (a) Chang, L.-X.; Xiong, G.; Wang, L.; Cheng, P.; Zhao, B. Chem. Commun. 2013, 49, 1055-1057. (b) Zheng, X.-Y.; Peng, J.-B.; Kong, X.-J.; Long, L.-S.; Zheng, L.-S. Inorg. Chem. Front. 2016, 3, 320–325. (c) Wu, M. Y.; Jiang, F. L.; Kong, X. J.; Yuan, D. Q.; Long, L. S.; Al-Thabaitic, S. A.; Hong, M. C. Chem. Sci. 2013, 4, 3104–3109. (d) Zhou, Y.; Zheng, X.-Y.; Cai, J.; Hong, Z.-F.; Yan, Z.-H.; Kong, X.-J.; Ren, Y.-P.; Long, L.-S.; Zheng, L.-S. Inorg. Chem. 2017, 56, 2037−2041. (e) Guo, F.-S.; Chen, Y.-C.; Mao, L.-L.; Lin, W.-Q.; Leng, J.-D.; Tarasenko, R.; Orendáč, M.; Prokleška, J.; Sechovsky, V.; Tong M.-L. Chem. Eur. J. 2013, 19, 14876 -14885. (f) Peng, J.-B.; Kong, X.-J.; Zhang, Q.-C.; Orendac, M.; Prokleska, J.; Ren, Y.-P.; Long, L.-S.; Zheng, Z.; Zheng, L.-S. J. Am. Chem. Soc. 2014, 136, 17938−17941. (g) Zheng, X.-Y.; Jiang, Y.-H.; Zhuang, G.-L.; Liu, D.-P.; Liao, H.-G.; Kong, X.-J.; Long, L.-S.; Zheng, L.-S. J. Am. Chem. Soc. 2017, 139, 18178-18181.

ACS Paragon Plus Environment

Page 4 of 5

Page 5 of 5 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

Journal of the American Chemical Society

Insert Table of Contents artwork here

ACS Paragon Plus Environment