Construction of the Lanthanide Diphosphonates via a Template

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Construction of the Lanthanide Diphosphonates via Template-Synthesis Strategy: Structures, Proton Conduction and Magnetic Behavior Jie Pan, Yu-Juan Ma, Song-De Han, Ji-Xiang Hu, Ying Mu, and Guo-Ming Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00293 • Publication Date (Web): 02 Apr 2019 Downloaded from http://pubs.acs.org on April 2, 2019

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Crystal Growth & Design

Construction of the Lanthanide Diphosphonates via Template-Synthesis Strategy: Structures, Proton Conduction and Magnetic Behavior

Jie Pan,† Yu-Juan Ma,† Song-De Han,† Ji-Xiang Hu,† Ying Mu,† Guo-Ming Wang*,† †

College of Chemistry and Chemical Engineering, Qingdao University, Shandong 266071, China

Supporting Information ABSTRACT: Two series of lanthanide phosphonates, [H4BAPEN]1.5·[Ln2(HEDP)3]·5H2O [Ln = Gd3+ (1-Gd), Tb3+ (1-Tb), Dy3+ (1-Dy)] and [H4BAPEN]0.5·[LnLi(HHEDP)2(H2O)2]·2H2O [Ln = Gd3+ (2-Gd), Tb3+ (2-Tb), Dy3+ (2-Dy)] (HEDP = 1hydroxyethylidenediphosphonate) displaying diverse structures have been successfully constructed templated by a protonated aliphatic organic amine 1,2-bis(3-aminopropylamino)ethane (BAPEN). The connection of Ln(III) ions and the diphosphonate ligand generates the one-dimensional (1D) chains for both series 1 and 2. Interestingly, 2D layered heterometallic diphosphonate networks were fabricated in series 2 wherein the adjacent Ln-HHEDP chains are joined together through the linkage of Li+. Notably, the compounds feature interesting proton conduction behavior. The conductivity increases smoothly with rising temperature, indicating that these compounds could act as promising candidates for temperature sensing. Moreover, the magnetic properties of them have been investigated.

INTRODUCTION As an important branch of inorganic-organic hybrid solids, metal phosphonates have aroused huge attention for not only their beautiful structures but promising properties in terms of photochemistry, proton conductivity, absorption, catalysis, magnetism, and so on.1-6 Compared with the plentiful molecules containing pyridyl or carboxylic groups which are usually employed for the generation of coordination polymers (CPs), the RPO32- group with at least three potential coordinating sites presents flexible and various coordination modes, leading to numerous compounds with diverse structures.7-9 However, the low solubility together with poor crystallinity of metal phosphonates put forward a great challenge to prepare superior crystalline products for acquiring their structures and investigating their properties. Recently, a common strategy to obtain corresponding crystals with suitable size for X-ray structural analysis has been widely acknowledged that modifying phosphonic acids with additional functional groups, including hydroxyl, amino, methyl and carboxyl groups.10-13 As a result, many fascinating metal phosphonates have been constructed and structurally characterized. For example, a rigid polyfunctional ligand with both phosphate and carboxyl groups was introduced to assist the fabrication of Ca-phosphonate framework for proton conductivity.14 Among the various approaches to the acquisition of these metal phosphonates, the structuredirecting agents (SDAs) or template strategy (amine, pyridine and their derivatives acting as the guest template) have been gradually used.15-17 The electronic and steric effects of various SDAs provide a great possibility to endow the directed metal phosphonates with novel architectures as well as promising properties, such as photochromism, ion-exchange and molecular recognition.

Lanthanide (Ln)-based compounds are of considerable interest and significant importance currently. On one hand, the Ln ions mainly with trivalent state can adopt various coordination numbers and geometries, thus could result in a wide variety of CPs bearing interesting structures with novelty and diversity when linking with different ligands. 18-20 On the other hand, the Ln-CP materials have been attached with great attention for their promising properties and applications in magnetism and photoluminescence areas. In particular, Ln(III) compounds could act excellent candidates for the generation of magnetic materials.21-25 By virtue of the unquenched orbital moment as well as strong spin-orbital coupling, several Ln(III) ions featuring large magnetic anisotropy have obvious advantage to obtain single-molecule magnets (SMMs) for molecular qubits, high-density information storage and spintronic devices. Dy(III)-based CPs, due to the multiple unpaired f-electrons as well as uniaxial anisotropy, are particularly significant as SMMs and representative of such materials.26-28 Apart from the interesting SMM behavior, magnetic refrigeration is also an important feature for Ln-CPs. On account of the traits of Gd(III) ions with high spin ground state, magnetic isotropy and weak exchange coupling, the Gd(III)-containing CPs are usually deemed to act as environmentally friendly solids for their feasible application as molecular coolants in magnetic refrigeration according to the magnetocaloric effect (MCE), leading to the imperative quest for the fabrication of novel molecular cryogenic magnetic coolers.29-31 In short, the exploration and investigation of Lnbased CPs is prospective for acquiring promising magnetic materials. Taking account of the aforementioned facts, we are investigating the combination of lanthanide ions with phosphonate to generate multifunctional materials with unique physical or chemical properties. As expected, two series of

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H have been refined anisotropic thermal parameters. 1898769 and 1898768 are the CCDC numbers for 1-Gd and 2-Gd. Detailed crystallographic data for Gd-based compounds are provided in Table 1. Table S1 lists some bond distances and angles for the Gd-based compounds.

lanthanide phosphonates were successfully constructed, [H4BAPEN]1.5·[Ln2(HEDP)3]·5H2O [Ln = Gd3+ (1-Gd), Tb3+ (1-Tb), Dy3+ (1-Dy)] and [H4BAPEN]0.5·[LnLi(HHEDP)2(H2O)2]·2H2O [Ln = Gd3+ (2Gd), Tb3+ (2-Tb), Dy3+ (2-Dy)] (BAPEN = 1,2-bis(3aminopropylamino)ethane, HEDP = 1hydroxyethylidenediphosphonate). Series 1 display an infinite one-dimensional (1D) Ln-HEDP chain with protonated organic amine acting as charge balancer and structural space filling. Series 2 feature the hetero-bimetallic phosphonates wherein the adjacent Ln-HHEDP chains are joined together through the linkage of Li+ to generate the 2D layer. Both the two series of compounds exhibit interesting proton conduction behavior. Moreover, the magnetic properties of them have been investigated.

Table 1 Crystallographic Data for Gd-based Compounds

EXPERIMENTAL SECTION Materials and methods. All chemical reagents were purchased with no any further purification. The Powder X-ray diffraction (PXRD) patterns have been performed from a Philips X’Pert-MPD diffractometer. The thermogravimetric (TG) curves were obtained from the NETZSCH STA 449 F5 instrument in 30 to 800 °C with N2 as inert gas. The Elemental Vario EL III instrument was employed to perform the data of elemental analysis for C, H, N. IR spectroscopy with KBr as pellets was carried out on a MAGNA-560 (Nicolet) FT-IR spectrometer. Magnetic data of the compounds were acquired from a Quantum Design SQUID (MPMS-XL-7) magnetometer. A Solartron 1287 electrochemical interface was utilized to investigate proton conduction behavior of the corresponding compounds. Synthesis of [H4BAPEN]1.5·[Ln2(HEDP)3]·5H2O [Ln = Gd3+ (1-Gd), Tb3+ (1-Tb), Dy3+ (1-Dy)]. The reaction condition of 1-Gd, 1-Tb and 1-Dy was similar, thus the synthesis of 1-Gd was provided in detail. 18.5 mg GdCl3·6H2O (0.5 mmol), 26 mg LiF (1 mmol), 0.5 mL H4HEDP (2.1 mmol), 0.65 mL BAPEN (4.6 mmol) and 8 mL H2O were mixed in a Teflonlined autoclave with the volume of 20 mL, then the content was kept at 145 °C for 120 hours followed by temperature cooling in 12 hours. Block colorless crystals could be obtained with a yield of 36%. Anal. Calcd for C18H61N6O26P6Gd2 (1278.04): C, 16.92; H, 4.81; N, 6.58. Found: C, 17.31; H, 4.62; N, 6.96. IR spectrum (ν/cm-1): 3385 (s), 2974 (m), 2365 (w), 1628 (m), 1521 (w), 1479 (w), 1323 (w), 1096 (s), 806 (w), 664 (w) (Figure S1). Synthesis of [H4BAPEN]0.5·[LnLi(HHEDP)2(H2O)2]·2H2O [Ln = Gd3+ (2-Gd), Tb3+ (2-Tb), Dy3+ (2-Dy)]. Synthesis of 2-Gd was provided as a representative. 37.1 mg GdCl3·6H2O (1 mmol), 102 mg LiF (4 mmol), 0.5 mL H4HEDP (2.1 mmol) and 0.2 mL BAPEN (1.4 mmol) in 8.0 mL distilled water was mixed together and kept at 145 °C for 5 days. Colorless sheet crystals could be harvested with the yield of 49% after cooling to ambient temperature for 12 hours. Anal. Calcd for C8H31N2O18P4GdLi (731.42): C, 13.14; H, 4.27; N, 3.83. Found: C, 13.55; H, 4.18; N, 3.76. IR spectrum (ν/cm-1): 3421 (s), 2960 (s), 2492 (w), 1621 (s), 1550 (m), 1507 (w), 1458 (w), 1330 (w), 1160 (s), 1054 (s), 997 (m), 827 (w), 657 (m). X-ray crystallography. Crystallographic data of Gd(III)based compounds was obtained from a Rigaku XtaLAB mini CCD diffractometer as the representatives. To solve the two structures, SHELX-2016 program was utilized. All atoms but

Compound

1-Gd

2-Gd

Empirical formula

C18H61N6O26P6Gd2

C8H31N2O18P4GdLi

Formula weight

1278.04

731.42

Crystal system

monoclinic

triclinic

Space group

P21/n

P-1

a (Å)

10.7472(4)

10.4376(8)

b (Å)

18.7169(6)

10.8263(9)

c (Å)

20.5610(8)

12.1354(12)

α()

90

65.135(9)

β (o)

102.084(4)

78.928(7)

γ (o)

90

68.876(7)

V (Å3)

4044.3(3)

1159.3(2)

Z

4

2

θ range (°)

2.92-32.31

2.85-30.69

R(int)

0.0271

0.0398

h, k, l, ranges

-12 to 8, -22 to 21, 15 to 24

-11 to 12, -12 to 12, -12 to 14

R1 , a wR2b (I >2σ( I))

0.0409, 0.0897

0.0375, 0.0841

GOF on F2

1.118

1.054

o

a

R = Σ(||Fo| - |Fc||)/Σ|Fo|. b Rw = {[Σw[(Fo2 - Fc2)2/Σw(Fo2)2]}1/2.

RESULTS AND DISCUSSION Crystal structure of [H4BAPEN]1.5·[Ln2(HEDP)3]·5H2O [Ln = Gd3+ (1-Gd), Tb3+ (1-Tb), Dy3+ (1-Dy)]. PXRD patterns (Figure S2) indicates the isostructure of compounds 1Gd, 1-Tb and 1-Dy, thus compound 1-Gd is selected to describe their structures as a representative example. 1-Gd belongs to monoclinic P21/n space group and presents a 1D chain structure. Its asymmetric unit contains two independent Gd(III) ions, three HEDP moieties, one and a half fully protonated H4BAPEN and five lattice water molecules (Figure 1a). Each Gd center features eight-coordinated configuration with a distorted triangular dodecahedron consisting of eight O atoms from six -PO3 groups of three HEDP ligands, with the Gd-O distance ranging from 2.281(4) to 2.637(9) Å. For these deprotonated HEDP, only four of oxygen atoms from -PO3 groups participate in coordination with bidentate mode to link with the Gd(III) center. There are two coordination types for HEDP: μ2-η2:η1: η1: η1:η0: η0 and μ2-η1:η1: η1: η1:η0: η0. As

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Figure 1. (a) The bridging environments for Gd(III) and the ligand in 1-Gd; (b) 1D waved-chain for 1-Gd; (c) and (d) view of the 3D supramolecule of 1-Gd along different directions.

Figure 2. (a) The bridging environments of metal ions and the ligand in 2-Gd; (b) the 2D layer constructed from the linkage of GdHHEDP chains and Li(I) ions; (c) and (d) perspective view of the 3D supramolecular framework of 2-Gd from different direction.



shown in Figure 1b, the HEDP groups bridge/chelate two Gd(III) ions giving rise to an infinite 1D chain, in which the separations of the neighboring Gd···Gd are 3.424 and 3.843 Å for 1-Gd. The uncoordinated amino and imino groups of BAPEN are protonated serving as a cationic species to neutralize the negative charge of the Gd-HEDP chain. Finally, neighboring 1D chains are stacked together via H-bond interaction (Table S2), fabricating a 3D supramolecular architecture, as clearly depicted in Figure 1c and 1d. Though the investigation of BAPEN-directed inorganic-organic hybrid materials have been widely reported accompanying with the development history of inorganic phosphites and phosphates, such as [Al(OH)(HPO3)2],32 [Zn2(HPO4)4],33 [Ga6F4(PO4)6]34 host directed by BAPEN, the long-chain flexible organic amine as the template to assist the construction of lanthanidephosphonate system is seldom reported.

seven-coordinated Gd(III) ions in 2-Gd are bridged by HHEDP ligands to form the linear chain with the Gd···Gd distance of 4.685 and 5.863 Å (Figure S4). Interestingly, the [LiO4] tetrahedron connects with the neighboring chains by Li-O bonds to generate a 2D negative layer (Figure 2b), wherein polygonal windows occupied by the protonated BAPEN molecules along [001] direction with the dimensions of 7.286 Å × 10.574 Å could be observed. Notably, the coordinated water protrudes outside of this layer, preventing the connection between neighboring layers to generate the 3D framework. To our knowledge, such 2D lanthanide-lithiumphosphonate anionic network directed by BAPEN has never been reported earlier to this work. As shown in Figure 2c and 2d, adjacent 2D sheets are further parallel packed into the resulting 3D supramolecular framework of 2-Gd by the Hbond (Table S3). Compared with the earlier reports on metal phosphonates with small rigid/flexible templates, such as [H2pip]3[Ge(hedp)2]·14H2O35 and [enH2]0.5Mn2[(HL)(L)],36 the employment of a long aliphatic amine BAPEN in the construction of metal-phosphonates provides a promising approach to prepare novel architectures.

Crystal structure of [H4BAPEN]0.5·[LnLi(HHEDP)2(H2O)2]·2H2O [Ln = Gd3+ (2-Gd), Tb3+ (2-Tb), Dy3+ (2-Dy)]. The structures of 2-Gd, 2Tb and 2-Dy are similar to each other (Figure S3), thus only 2-Gd is discussed as a representative in detail. Compound 2Gd features a 2D heterometallic phosphonate architecture. It belongs to triclinic P-1 space group with one Gd(III) ion, one Li(I) ion, two HHEDP (partially deprotonated H4HEDP) ligands, one half protonated H4BAPEN, four water molecules (two coordinated and two free) residing in its asymmetry unit. In the crystal structure of 2-Gd, the unique Gd(III) ion is seven-coordinated in a monocapped octahedron configuration defined by seven O atoms from four distinct HHEDP ligands as depicted in Figure 2a. For Li(I) center, it is four-connected and adopts a tetrahedral geometry with two oxygen atoms from a pair of HHEDP units, leaving the other two coordination sites for two water molecules. One of the HHEDP displays the μ3-η1:η1:η1:η1:η0:η0 coordination fashion bridging three metal centers via O1, O2 and O3 atoms from the -PO3 group and O4 of -HPO3 group, and the other one takes its O7, O8 as well as O10-O12 atoms to coordinate to three metal ions. Gd1 and its symmetric one are held together by two HHEDP ligands, forming a dimeric [Gd 2(HHEDP)2] building unit. Each binuclear subunit connects with two identical ones through sharing oxygen atoms of HHEDP, leading to the formation of a 1D Gd-HHEDP inorganicorganic chain. Distinct from the 1D waved-chain of 1-Gd,

PXRD patterns and thermostability. To further confirm the phase purity of solids series 1 and 2, PXRD analysis was performed. As displayed in Figures S2-S3, the main peak positions of the theoretical patterns match well with the experimental ones, indicating the homogeneity of the two series of samples as well as the high purity of all the bulk solids. TG measurements of compounds 1-Gd and 2-Gd were performed up to 800 °C with N2 as protective gas to assess the thermal stability of these lanthanide phosphonate CPs. As shown in Figure S5, the TG curves revealed that compound 1Gd displays a 7.25% weight loss (calcd. 7.05%) in 25-140 °C, in agreement with the loss of five free water molecules per formula. The main host can remain its stability to 315 °C and then begins to collapse with the loss of organic components. Compound 2-Gd displays a weight loss of 9.93% (calcd, 9.85%) between 25-187 °C for all the water molecules. Then the dehydrated framework of 2-Gd maintains its skeleton to 280 °C with no any further loss of weight. With the increase of temperature, an obvious weight loss process could be observed, which probably due to the decomposition of the organic moieties.

Figure 3. The Nyquist plots of compounds 1-Gd (a) and 2-Gd (b) at different temperatures under 100% relative humidity.


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Figure 4. χT vs. T and χ−1 vs. T plots for 1-Gd (a) and 2-Gd (b) (red solid line for Curie-Weiss fitting).

variable-temperature magnetic susceptibilities have been displayed in Figure 4. The χT values are 15.41 and 7.90 cm3 K mol−1 for 1-Gd and 2-Gd at 300 K, matching well with the expected value for one and two isolated Gd3+ ion (8S7/2, S = 7/2, g = 2, C = 7.88 cm3 K mol−1), respectively.45-47 After a slow decrease with lowering temperatures, the χT values sharply drop to the minimum value of 10.81 and 7.25 cm 3 K mol−1 for the two compounds at 2 K. This phenomenon is mainly due to the depopulation of excited Stark levels of Gd 3+ ions, or the antiferromagnetic magnetic interactions between intrachain Gd3+ centers.48,49 The magnetic susceptibility data are also fitted by Curie-Weiss law exhibiting the Curie constant C of 15.39, 7.88 cm3 K mol−1 and Curie temperature θ of -1.52, 0.34 K for 1-Gd and 2-Gd, respectively. The negative θ values further support the intrachain antiferromagnetic interactions. Isothermal field dependence of the magnetization measurements is investigated in the field range of 0-50 kOe at 2 K. Both magnetization curves exhibit the linear increase at the low field, then achieve the maximum values of 13.88 and 7.10 Nβ at 50 kOe (Figure S8-S9), which are very close to the expected value of 14.0 for two and 7.0 Nβ for one Gd 3+ ions.

Proton conductivity and magnetic properties. The protonated amines (H4BAPEN) in compounds 1-Gd and 2-Gd can be considered as the proton carriers. H-bond can be found between H4BAPEN and the phosphonate oxygen as well as between the guest water molecules and phosphonate hydroxyl for both the two compounds (Table S2-S3) and those adsorbed water molecules could generate the H-bonding chains with bridging oxygen and diphosphonate ligands serving as protonconducting pathways.4,37-42 Therefore, the proton conduction behavior of these Gd-based compounds have been studied by Nyquist plots. Compounds 1-Gd and 2-Gd show interesting humidity dependence behavior on proton conductivity. Neither of them is found with conductivity at ambient temperature and humidity, probably due to the absence of effective path for proton conduction. After putting the samples for 12 hours in saturated water vapor, the conductivity of compounds 1-Gd and 2-Gd becomes to be 1.64 × 10-4 S cm-1 and 2.07 × 10-4 S cm-1, respectively. This phenomenon can be attributed to the reason that numerous water molecules enter into the structures to form new H-bond and further promote the transport of protons, thus leading to the increase of conductivity with humidity increasing. As depicted in Figure 3, the impedance as a function of temperature was performed under 100% relative humidity. The bulk and grain boundary impedances are represented by semicircle, and the accumulation of ionic charges such as proton species are shown with small tail at low frequency. The conductivity of Gd-based compounds both increase gradually with the temperature being elevated, and finally reach to 6.47 ×10-4 and 3.75 ×10-4 S cm-1 at 90 and 95 °C, respectively, which are comparable to many reported proton-conductive materials, such as {[Gd(MA)(Ox)(H2O)]n·3H2O},43 [Cd(HDMPhIDC)(H2O)]n,44 indicating that these compounds could act as promising candidates for temperature sensing. The PXRD curves for 1Gd and 2-Gd match with their simulated ones (Figures S6 and S7) after proton conduction experiment, indicating the structural stability during the measurement process. The magnetic properties of the two Gd(III)-based compounds are investigated from 2 K to 300 K, and their

CONCLUSIONS The linkage of Ln(III) ions with 1hydroxyethylidenediphosphonate has afforded two series of lanthanide phosphonates templated by a protonated flexible aliphatic amine. The protonated guest here not only acts as a charge balancer and space filling but serves as the structuredirecting agent to generate diverse architectures. Interestingly, Li+ was introduced to assist the fabrication of a 2D heterometallic phosphonate in this work. Both the series compounds display proton conduction behavior, as the conductivity increases with the elevated temperature. Adding with their magnetic properties, the assembly of lanthanide phosphonates may provide a promising approach to develop novel multifunctional materials.



ASSOCIATED CONTENT Supporting Information. Some bond distances and angles for 1Gd and 2-Gd, details of hydrogen bond, PXRD, TG curves and additional figures. CCDC 1898769 and 1898768 for 1-Gd and 2Gd.

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AUTHOR INFORMATION Corresponding Author

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*E-mail: [email protected]. Notes

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The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS We are thankful to the support from National Natural Science Foundation of China (21571111, 21601100).

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REFERENCES (1)

(2)

(3)

(4)

(5)

(6)

(7) (8) (9)

(10)

(11)

(12)

(13)

(14)

(20)

Zhang, R.; Russo, P. A.; Buzanich, A. G.; Jeon, T.; Pinna, N. Hybrid Organic-Inorganic Transition-Metal Phosphonates as Precursors for Water Oxidation Electrocatalysts. Adv. Funct. Mater. 2017, 27, 1703158. Ma, Y. J.; Han, S. D.; Pan, J.; Mu, Y.; Li, J. H.; Wang, G. M. An Inorganic–Organic Hybrid Framework from the Assembly of an Electron-Rich Diphosphonate and Electron-Deficient Tripyridyl Moiety. J. Mater. Chem. C 2018, 6, 9341-9344. Yang, W.; Tian, H. R.; Li, J. P.; Hui, Y. F.; He, X.; Li, J.; Dang, S.; Xie, Z.; Sun, Z. M. Photochromic Terbium Phosphonates with Photomodulated Luminescence and Metal Ion Sensitive Detection. Chem. Eur. J. 2016, 22, 15451-15457. Bao, S. S.; Shimizu, G. K. H.; Zheng, L. M. Proton Conductive Metal Phosphonate Frameworks. Coord. Chem. Rev. 2019, 378, 577-594. Li, H.; Sun, Y.; Yuan, Z. Y.; Zhu, Y. P.; Ma, T. Y. Titanium Phosphonate Based Metal–Organic Frameworks with Hierarchical Porosity for Enhanced Photocatalytic Hydrogen Evolution. Angew. Chem. Int. Ed. 2018, 57, 3222-3227. Yang, F.; Xu, G.; Dou, Y.; Wang, B.; Zhang, H.; Wu, H.; Zhou, W.; Li, J. R.; Chen, B. A Flexible Metal-Organic Framework with a High Density of Sulfonic Acid Sites for Proton Conduction. Nat. Energy 2017, 2, 877-883. Goura, J.; Chandrasekhar, V. Molecular Metal Phosphonates. Chem. Rev. 2015, 115, 6854-6965. Bao, S. S.; Zheng, L. M. Magnetic Materials Based on 3d Metal Phosphonates. Coord. Chem. Rev. 2016, 319, 63-85. Zheng, T.; Yang, Z.; Gui, D.; Liu, Z.; Wang, X.;Dai, X.; Liu, S.; Zhang, L.; Gao, Y.; Chen, L.; Sheng, D.; Wang, Y.; Diwu J.; Wang, J.; Zhou, R.; Chai, Z.; Albrecht-Schmitt T. E.; Wang, S. Overcoming the Crystallization and Designability Issues in the Ultrastable Zirconium Phosphonate Framework System. Nat. Commun. 2017, 8, 15369. Fu, R.; Hu, S.; Wu, X. Rapid and Sensitive Detection of Nitroaromatic Explosives by Using New 3D Lanthanide Phosphonates. J. Mater. Chem. A 2017, 5, 1952-1956. Fu, R.; Hu, S.; Wu, X. Luminescent Zinc Phosphonates for Ratiometric Sensing of 2,4,6-Trinitrophenol and Temperature. Cryst. Growth Des. 2016, 16, 5074-5083. Taddei, M.; Sassi, P.; Costantino, F.; Vivani, R. AminoFunctionalized Layered Crystalline Zirconium Phosphonates: Synthesis, Crystal Structure, and Spectroscopic Characterization. Inorg. Chem. 2016, 55, 6278-6285. Xu, H.; Zhou, H.; Feng, L.; Wang, Q.; Chen, R.; Huang, W.; Wu, X. Synthesis, Crystal Structures, and Magnetic Properties of Six Transition Metal Phosphonates. Dalton Trans. 2018, 47, 1122611238. Bazaga-García, M.; Colodrero, R. M. P.; Papadaki, M.; Garczarek, P.; Zoń, J.; Olivera-Pastor, P.; Losilla, E. R.; León-Reina, L.; Aranda, M. A. G.; Choquesillo-Lazarte, D.; Demadis, K. D.; Cabeza,

(21)

(22)

(23)

(24)

(25)

(26)

(27)

(28) (29)

(30)

(31)

(32)

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A. Guest Molecule-Responsive Functional Calcium Phosphonate Frameworks for Tuned Proton Conductivity. J. Am. Chem. Soc. 2014, 136, 5731-5739. Ma, Y. J.; Han, S. D.; Mu, Y.; Pan, J.; Li, J. H.; Wang, G. M. Two Cobalt-Diphosphonates Templated by Long-Chain Flexible Amines: Synthesis, Structures, Proton Conductivity, and Magnetic Properties. Cryst. Growth Des. 2018, 18, 3477-3483. Li, J. H.; Han, S. D.; Pan, J.; Xue, Z. Z.; Wang, G. M.; Wang, Z. H.; Bao, Z. Z. Template Synthesis and Photochromism of a Layered Zinc Diphosphonate. CrystEngComm 2017, 19, 1160-1164. Paul, A. K.; Kanagaraj, R.; Jana, A. K.; Maji, P. K. Novel Amine Templated Three-Dimensional Zinc-Organophosphonates with Variable Pore-Openings. CrystEngComm 2017, 19, 6425-6435. Yang, Y.; Jiang, F.; Liu, C.; Chen, L.; Gai, Y.; Pang, J.; Su, K.; Wan, X.; Hong, M. Self-Assembly Syntheses, Structural Characterization, and Luminescent Properties of Lanthanide Coordination Polymers Constructed by Three Triazole-Carboxylate Ligands. Cryst. Growth Des. 2016, 16, 2266-2276. Cui, C.; Ju, W.; Luo, X.; Lin, Q.; Cao, J.; Xu, Y. A Series of Lanthanide Compounds Constructed from Ln8 Rings Exhibiting Large Magnetocaloric Effect and Interesting Luminescence. Inorg. Chem. 2018, 57, 8608-8614. Yang, Y.; Chen, L.; Jiang, F.; Wu, M.; Pang, J.; Wan, X.; Hong, M. A Water-Stable 3D Eu-MOF Based on a Metallacyclodimeric Secondary Building Unit for Sensitive Fluorescent Detection of Acetone Molecules. CrystEngComm 2019, 21, 321-328. Liu, K.; Zhang, X.; Meng, X.; Shi, W.; Cheng, P.; Powell, A. K. Constraining the Coordination Geometries of Lanthanide Centers and Magnetic Building Blocks in Frameworks: a New Strategy for Molecular Nanomagnets. Chem. Soc. Rev. 2016, 45, 2423-2439. Mayans, J.; Saez, Q.; Font-Bardia, M.; Escuer, A. Enhancement of Magnetic Relaxation Properties with 3d Diamagnetic Cations in [ZnIILnIII] and [NiIILnIII], LnIII = Kramers Lanthanides. Dalton Trans. 2019, 48, 641-652. Wong, H. Y.; Chan, W. T. K.; Law, G. L. Assembly of Lanthanide(III) Cubanes and Dimers with Single-Molecule Magnetism and Photoluminescence. Inorg. Chem. 2018, 57, 68936902. Krylov, D. S.; Liu, F.; Avdoshenko, S. M.; Spree, L.; Weise, B.; Waske, A.; Wolter, A. U. B.; Büchner, B.; Popov, A. A. RecordHigh Thermal Barrier of the Relaxation of Magnetization in the Nitride Clusterfullerene Dy2ScN@C80-Ih. Chem. Commun. 2017, 53, 7901-7904. Liu, J. L.; Chen, Y. C.; Tong, M. L. Symmetry Strategies for High Performance Lanthanide-Based Single-Molecule Magnets. Chem. Soc. Rev. 2018, 47, 2431-2453. Tian, H.; Su, J. B.; Bao, S. S.; Kurmoo, M.; Huang, X. D.; Zhang, Y. Q.; Zheng, L. M. Reversible ON–OFF Switching of SingleMolecule-Magnetism Associated with Single-Crystal-to-SingleCrystal Structural Transformation of a Decanuclear Dysprosium Phosphonate. Chem. Sci. 2018, 9, 6424-6433. Chen, Y. C.; Liu, J. L.; Ungur, L.; Liu, J.; Li, Q. W.; Wang, L. F.; Ni, Z. P.; Chibotaru, L. F.; Chen, X. M.; Tong, M. L. SymmetrySupported Magnetic Blocking at 20 K in Pentagonal Bipyramidal Dy(III) Single-Ion Magnets. J. Am. Chem. Soc. 2016, 138, 28292837. Woodruff, D. N.; Winpenny, R. E. P.; Layfield, R. A. Lanthanide Single-Molecule Magnets. Chem. Rev. 2013, 113, 5110-5148. Han, Y.; Han, S. D.; Pan, J.; Ma, Y. J.; Wang, G. M. An Excellent Cryogenic Magnetic Cooler: Magnetic and Magnetocaloric Study of an Inorganic Frame Material. Mater. Chem. Front. 2018, 2, 23272332. Zheng, X. Y.; Kong, X. J.; Zheng, Z.; Long, L. S.; Zheng, L. S. High-Nuclearity Lanthanide-Containing Clusters as Potential Molecular Magnetic Coolers. Acc. Chem. Res. 2018, 51, 517-525. Song, T. Q.; Dong, J.; Yang, A. F.; Che, X. J.; Gao, H. L.; Cui, J. Z.; Zhao, B. Wheel-like Ln18 Cluster Organic Frameworks for Magnetic Refrigeration and Conversion of CO2. Inorg. Chem. 2018, 57, 3144-3150. Xiang, Y.; Zhang, L. W.; Chen, W. H.; Chen, J. Z.; Zeng, Q. X. Synthesis and Characterization of a New Organically Templated Aluminophosphite with a Chainlike Structure. Z. Anorg. Allg. Chem. 2007, 633, 1727-1730.


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(33) Mandal, S.; Natarajan, S. Solvothermal Synthesis and Structures of One- and Two-Dimensional Zinc Phosphates. Inorg. Chim. Acta 2004, 357, 1437-1443. (34) Ramaswamy, P.; Mandal, S.; Natarajan, S. New Open-Framework Phosphate and Phosphite Compounds of Gallium. Inorg. Chim. Acta 2011, 372, 136-144. (35) Rocha, J.; Shi, F. N.; Paz, F. A. A.; Mafra, L.; Sardo, M.; CunhaSilva, L.; Chisholm, J.; Ribeiro-Claro, P.; Trindade, T. 3D-2D-0D Stepwise Deconstruction of a Water Framework Templated by a Nanoporous Organic-Inorganic Hybrid Host. Chem. Eur. J. 2010, 16, 7741-7749. (36) Dong, D. P.; Sun, Z. G.; Tong, F.; Zhu, Y. Y.; Chen, K.; Jiao, C. Q.; Wang, C. L.; Li, C.; Wang, W. N. Synthesis, Structure, Surface Photovoltage and Magnetic Properties of a Novel 3D Homochiral Manganese Phosphonate with Right-handed Helical Chains. CrystEngComm 2011, 13, 3317-3320. (37) Wu, H.; Yang. F.; Lv, X. L.; Wang, B.; Zhang, Y. Z.; Zhao, M. J.; Li, J. R. A Stable Porphyrinic Metal-Organic Framework PoreFunctionalized by High-Density Carboxylic Groups for Proton Conduction. J. Mater. Chem. A 2017, 5, 14525-14529. (38) Yang, F.; Huang, H.; Wang, X.; Li, F.; Gong, Y.; Zhong, C.; Li, J. R. Proton Conductivities in Functionalized UiO-66: Tuned Properties, Thermogravimetry Mass, and Molecular Simulation Analyses. Cryst. Growth Des. 2015, 15, 5827-5833. (39) Yoon, M.; Suh, K.; Natarajan, S.; Kim, K. Proton Conduction in Metal-Organic Frameworks and Related Modularly Built Porous Solids. Angew. Chem. Int. Ed. 2013, 52, 2688-2700. (40) Sun, Z.; Yu, S.; Zhao, L.; Wang, J.; Li, Z.; Li, G. A Highly Stable Two-Dimensional Copper(II) Organic Framework for Proton Conduction and Ammonia Impedance Sensing. Chem. Eur. J. 2018, 24, 10829-10839. (41) Liu, R.; Zhao, L.; Yu, S.; Liang, X.; Li, Z.; Li, G. Enhancing Proton Conductivity of a 3D Metal-Organic Framework by Attaching Guest NH3 Molecules. Inorg. Chem. 2018, 57, 11560-11568. (42) Xiao, C.; Wang, Y.; Chen, L.; Yin, X.; Shu, J.; Sheng, D.; Chai, Z.; Albrecht-Schmitt, T. E.; Wang S. Boosting Proton Conductivity in

(43)

(44)

(45)

(46)

(47)

(48)

(49)

Highly Robust 3D Inorganic Cationic Extended Frameworks through Ion Exchange with Dihydrogen Phosphate Anions. Chem. Eur. J. 2015, 21, 17591-17595. Biswas, S.; Chakraborty, J.; Parmar, V. S.; Bera, S. P.; Ganguli, N.; Konar, S. Channel-Assisted Pronton Conduction Behavior in Hydroxyl-Rich Lanthanide-Based Magnetic Metal-Organic Frameworks. Inorg. Chem. 2017, 56, 4956-4965. Xie, X.; Yu, S.; Yang, C.; Zhang, J.; Li, Z.; Li, G. Iron(III) identification and Proton Conduction of a Luminescent CadmiumOrganic Framework. New J. Chem. 2018, 42, 20197-20204. Li, Z. Y.; Zhai, B.; Li, S. Z.; Cao, G. X.; Zhang, F. Q.; Zhang, X. F.; Zhang, F. L.; Zhang, C. Two Series of Lanthanide Coordination Polymers with 2-Methylenesuccinate: Magnetic Refrigerant, Slow Magnetic Relaxation, and Luminescence Properties. Cryst. Growth Des. 2016, 16, 4574-4581. Machata, M.; Herchel, R.; Nemec, I.; Trávníček, Z. Crystal Structures and Magnetic Properties of Two Series of Phenoxo-O Bridged Dinuclear Ln2 (Ln = Gd, Tb, Dy) Complexes. Dalton Trans. 2017, 46, 16294-16305. Yao, S. L.; Cao, C.; Tian, X. M.; Zheng, T. F.; Liu, S. J.; Tong, X. L.; Liao, J. S.; Chen, J. L.; Wen, H. R. Three Gd-Based Metal-Organic Frameworks Constructed from Similar Dicarboxylate Ligands with Large Magnetic Entropy Changes. ChemistrySelect 2017, 2, 1067310677. Pointillart, F.; Guennic, B. L.; Golhen, S.; Cador, O.; Maury, O.; Ouahab, L. A Redox-Active Luminescent Ytterbium Based Single Molecule Magnet. Chem. Commun. 2013, 49, 615-617. Hu, F. L.; Jiang, F. L.; Zheng, J.; Wu, M. Y.; Pang, J. D.; Hong, M. C. Magnetic Properties of 3D Heptanuclear Lanthanide Frameworks Supported by Mixed Ligands. Inorg. Chem. 2015, 54, 6081-6083.



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Manuscript title: Construction of the Lanthanide Diphosphonates via Template-Synthesis Strategy: Structures, Proton Conduction and Magnetic Behavior Author list: Jie Pan, Yu-Juan Ma, Song-De Han, Ji-Xiang Hu, Ying Mu, Guo-Ming Wang*

Synopsis: Two series of lanthanide diphosphonates templated by a protonated flexible aliphatic amine were constructed with proton conduction behavior and magnetic properties.

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Construction of the Lanthanide Diphosphonates via a Template

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