Two Cobalt-diphosphonates Templated by Long-Chain Flexible Amines

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Two cobalt-diphosphonates templated by long-chain flexible amines: synthesis, structures, proton conductivity and magnetic properties Yu-Juan Ma, Song-De Han, Ying Mu, Jie Pan, Jin-Hua Li, and Guo-Ming Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00225 • Publication Date (Web): 16 Apr 2018 Downloaded from http://pubs.acs.org on April 17, 2018

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Crystal Growth & Design

Two cobalt-diphosphonates templated by long-chain flexible amines: synthesis, structures, proton conductivity and magnetic properties Yu-Juan Ma,† Song-De Han,† Ying Mu,† Jie Pan,† Jin-Hua Li,† and Guo-Ming Wang*,† †

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

Supporting Information Placeholder ABSTRACT: Two new cobalt-diphosphonates templated by protonated 1,2-bis(3-aminopropylamino)ethane (BAPEN), (C8N4H26)0.5·[Co(HEDP)]·H2O (1) and (C8N4H26)·[Co2(HEDP)2(H2O)2]·5H2O (2) were hydrothermally prepared (HEDP = CH3C(OH)(PO3)2, 1-hydroxyethylidenediphosphonate). Compounds 1 and 2 exhibit anionic 1D Co-HEDP chain and 2D Co-HEDP layer structure, respectively. The structure diversities from 1D chain to 2D layer was realized by adjusting the synthetic parameters. Their magnetism and proton conduction have been studied. Magnetic measurements indicated that the title compounds exhibits weak magnetic interactions. Compounds 1 and 2 feature a proton conductivity of 3.57 × 10-4 and 9.43 × 10-5 S cm−1 at 100% relative humidity and 65 °C, respectively.

Introduction Metal-phosphonates have attracted huge attention of researchers because of their appealing structures and physicochemical properties.1-9 The sound assembly of suitable homometallic (or heterometallic) ions and organophosphonates (from mono-phosphonate and polyphosphonate to other functionalised phosphonates) generated lots of fascinating products, which offers opportunity for the generation of molecule-based materials with desirable structure (from isolated clusters to chains and coordination network) and properties (catalysis, luminescence, adsorption, magnetism, etc.).1-20 The organoamine-directed synthetic strategy is efficient to the fabrication of crystalline materials.21-23 The organoaminedirected assembly has been widely investigated in the development history of phosphate and phosphite.24-28 The template role together with the potential coordination role of organoamine provides the opportunities for fabricating exotic products in terms of structure and properties. Considering the similarity between inorganic phosphates (or phosphites) and organophosphonates, the organoamines-directed assembly is also applicable to the metal phosphonate. An overview of literature indicated that the early investigated organoamines mainly focus on the small rigid/flexible species, just exampled by heterocyclic amine and aliphatic amine.29-34 By contrast, the long aliphatic amine (the total atoms for the chain larger than eight)35-39 and large heterocyclic amine (the N-heterocycle larger than three) are relatively less investigated.40-45 This is not surprising for several reasons, one of which may be partly due to the fact that such long-chain flexible organic amines are easily decomposed under hydrothermal conditions. We have demonstrated that grafting N-heterocyclic amine to metal-phosphonates would generate a series of novel resulting products.46-49 Our previous works mainly focus on metalphosphonate directed by the rigid N-heterocyclic amine.46-48 For example, utilising the protonated tripyridine moiety as template, we made a 2D zincodiphosphonate with rapid photochromism.46 Two layered zinc diphosphonates was

produced by utilising the coordination role and template rule of bipyridine moiety.47 Two transition metal-triphosphonates layer pillared by triimidazoe unit have also been synthesized.48 As continuous search for new metal-phosphonate, we attempted to, in this work, introduce the long-chain flexible aliphatic amine, 1,2-bis(3-aminopropylamino)ethane (BAPEN), into the cobalt-HEDP ([CH3C(OH)(PO3)2], 1hydroxyethylidenediphosphonate) system (Scheme 1), based on the following considerations: (a) as a multi-dentate ligand, HEDP has been intensively utilised to generate phosphonates containing captivating structures and/or properties;39,50-53 (b) the cobalt(II) ion with large single-ion anisotropy is a promising spin carrier for the generation of metal-phosphate bearing fascinating magnetism;4 (c) the metal-phosphonate is an excellent platform for searching structure with high proton conductivity due to their excellent thermal and chemical stabilities and rich guest-host chemistry.54,55 Herein, we report two protonated BAPEN-directed cobaltdiphosphonates, (C8N4H26)0.5·[Co(HEDP)]·H2O (1) and (C8N4H26)·[Co2(HEDP)2(H2O)2]·5H2O (2). 1 and 2 show anionic Co-HEDP chain and Co-HEDP layer structure, respectively. The structure diversities from 1D chain to 2D layer was observed by mediating the synthetic parameters. Their magnetism and proton conduction are studied.

Scheme 1. 1,2-bis(3-aminopropylamino)ethane (BAPEN) and diphosphonate (HEDP).

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(C8N4H26)·[Co2(HEDP)2(H2O)2]·5H2O (2) Mixing CoSO4 (0.28 g, 1.00 mmol), BAPEN (0.30 mL, 1.64 mmol), HEDP (0.28 mL, 1.97 mmol) and H2O (10 mL) in an 25mL Teflon-lined autoclave, and heating at 145 °C for 120 hours and then cooling to room temperature. Yield: ca. 65% based on HEDP. Theoretical EA (%) for C12H48N4O21P4Co2 (826.28): C, 17.44; H, 5.86; N, 6.78. Found: C, 17.72; H, 6.15; N, 6.47. IR (cm–1): 3408(s), 2972(m), 2366(w), 1629(s), 1528(w), 1474(w), 1402(w), 1082(s), 946(s), 826(s), 754(w), 666(m), 574(s), 474(m).

Experimental Section Materials and Physical measurements All chemicals were analytical grade without additional purification. Powder X-ray diffraction (PXRD) plot was measured on a SmartLab X-ray diffractometer (Rigaku). Simulated PXRD plot was generated from the corresponding cif file by the Hg-soft. Thermogravimetric (TG) analysis was measured on a Rigaku standard TG-DTA analyzer. Elemental analysis (EA) was measured on a Perkin-Elmer 240C analyzer. IR spectroscopy was measured on a MAGNA-560 (Nicolet) FT-IR spectrometer with KBr as pellets. The magnetic data were measured on PPMS DynaCool Cryogen-free System. The diamagnetic corrections were finished with Pascal's constants. The proton conduction was measured on Solartron 1287 electrochemical interface coupled with 1260 frequency response analyzer. The resistance was simulated from the Nyquist plot. The conductivities were derived from the formula: σ = D/(R*S) (D, S and R represent the thickness, cross-sectional area and bulk resistance of the sample tablets.

Structural Characterization The SCXRD data were collected on a XtaLAB-mini diffractometer at 293(2) K with Mo-Kα radiation (λ = 0.71073 Å) by ω scan mode. The structures were determined by SHELX-2016 software.56 The main crystallographic parametes are provided in Table 1. CCDC Nos. 1814413 for 1 and 1814414 for 2 contain the full crystallographic data.

Results and Discussion Description of crystal structure

Table 1. Crystallographic data for the title compounds.

Formula Fw T/K λ/Å Crystal system Space group a/Å b/Å c/Å α/° β/° γ/° V/Å3 Z Dc/g cm-3 µ/mm−1 F (000) total reflns unique reflns Rint Final R indices [I>2σ(I)] wR2 (all data) GOF on F2

1 C6H19N2O8P2Co 368.10 293(2) 0.71073 Triclinic P-1 5.4490(6) 11.0890(10) 11.7483(14) 109.514(9) 94.564(9) 102.987(8) 642.68(13) 2 1.902 1.621 380 3308 2272 0.0295 R1 = 0.0571 wR2 = 0.1491 R1 = 0.0733 wR2 = 0.1648 1.053

Compound 1 crystallizes in the space group of Pī. There are one crystallographically independent Co atom, one HEDP molecules, half a free protonated organoamine molecule and one free water molecule in the asymmetric unit. All Co atoms are in the [CoO6] octahedral geometry (Figure 1a), which are offered by five phosphonate oxygen atoms and one hydroxyl oxygen from three symmetry-related HEDP ligands. Each HEDP ligand acts as chelating-bridging ligand to connect three symmetry-related Co1 atoms. The Co-O bond lengths range from 2.032(4) to 2.258(3) Å. The O-Co-O bond angles are in the scope 77.86(13)-174.15(13)°. The alternating arrangement of Co atoms and HEDP ligand gives rise to the anionic 1D chain of 1 (Figure 1b) with the protonated organoamine (H4-BAPEN) as charge-balancer. The H4BAPEN molecules lie in the interchain voids and interact with the chain via H-bonds (N-H⋅⋅⋅O) (Figure 1c, 1d, Table S3). The space group of compound 2 is P21/c. There are two Co atoms, two HEDP molecules, two coordinated water molecules, one free protonated organoamine molecule and five lattice water molecules in the asymmetrical unit. Co1 has a hexa-coordinate [CoO6] environment from five phosphonate oxygen atoms and one hydroxyl oxygen from three symmetryrelated HEDP ligands, exhibiting a distorted octahedral geometry (Figure 2a). Co2 also has a hexa-coordinate [CoO6] environment. Four O-atoms from two symmetry-related HEDP groups fill the equatorial positions and two coordinated water molecules occupy the axial positions (Figure 2a). Each crystallographically independent HEDP unit chelates and bridges Co atoms. HEDP1 containing P1 and P2 atoms connect two independent Co atoms (Co1 and Co2), while HEDP2 containing P3 and P4 atoms connect two symmetryrelated Co1 atoms and one Co2 atom. The Co-O bond lengths are in the scope 2.031(3) to 2.325(3) Å. The O-Co-O bond angles range from 76.78(10)-179.21(12)°. The alternating arrangement of Co atoms and HEDP ligand results in a 16membered ring (16-MR) (Figure 2b), which acts as supramolecular building blocks to form anionic 2D layer via sharing the phosphonate oxygen (Figure 2c). The negative charge of the layer is balanced by the protonated organoamine

2 C12H48N4O21P4Co2 826.28 293(2) 0.71073 Monoclinic P21/c 10.5158(6) 18.9596(11) 14.9538(9) 90 104.814(6) 90 2882.3(3) 4 1.904 1.469 1720 10646 5080 0.0313 R1 = 0.0435 wR2 = 0.1206 R1 = 0.0608 wR2 = 0.1314 1.070

Preparation of (C8N4H26)0.5·[Co(HEDP)]·H2O (1) Mixing CoCl2 (0.12 g, 0.50 mmol), BAPEN (0.40 mL, 2.18 mmol), HEDP (0.30 mL, 2.11 mmol) and H2O (8 mL) in an 25mL Teflon-lined autoclave, and heating at 145 °C for 120 hours and then cooling to room temperature. Yield: ca. 50% based on HEDP. Theoretical EA (%)for C6H19N2O8P2Co (368.10): C, 19.58; H, 5.20; N, 7.61. Found: C, 19.82; H, 5.46; N, 7.23. IR (cm–1): 3408(s), 2972(m), 2366(w), 1618(s), 1552(w), 1474(w), 1396(m), 1316(w), 1274(w), 1094(s), 962(w), 886(w), 806(m), 666(m), 596(s), 554(w).

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Figure 1. (a) Coordination modes of Co ions in 1. (b) Ball-stick view of 1D chain. The packing structural modes of 1 along b axis (c) and a axis (d).

(H4-BAPEN). The H4-BAPEN molecules are located in the pores of 16-MR of the 2D layer and interact with the layer via H-bonds (N-H⋅⋅⋅O) (Figure 2d, Table S4). Although the structural constituents of compounds 1 and 2 are same (H4-BAPEN as guest, HEDP and Co(II) as host), they display obviously distinct structural characteristics (1D chain for 1 and 2D layer for 2). The structural modulation from 1D chain to 2D layer was achieved by adjusting the synthetic parameters, which gives us a hint that structural diversities for metal-phosphonate directed by H4-BAPEN may be realized via tuning the synthetic conditions.

protonated BAPEN (cal: 21.58%). Further heating from 610 °C causes the frame to collapse. The peaks of experimental PXRD plots are in agreement with the simulated ones from SCXRD (Figure S2, S3), indicative of the purity of 1 and 2.

Magnetic and proton conductivity studies All magnetic characterizations were measured on crushed crystalline samples. The variable-temperature magnetic susceptibility was investigated in the range 2–300 K with a 1000 Oe applied filed. As shown in Figure 3a, the experimental χMT values of 4.32 and 6.43 cm3 K mol-1 at 300 K for 1 and 2 exceed the calculated ones for the unit of noninteracting Co(II) (1.88 cm3 K mol-1 for 1; 3.75 cm3 K mol-1 for 2, with S = 3/2 and g =2 per Co(II) ion), which is due to the strong orbital contributions of the octahedral Co(II) ions.57,58 During cooling, the χMT product of 1 and 2 slowly declines from 300 K to 50 K, with a rapid decline to the minimum value of 0.16 cm3 K mol-1 for 1 and 1.33 cm3 K mol-1 for 2 at 2 K. The negative Weiss constant θ from Curie–Weiss fitting is − 23.33 K for 1 and − 10.23 K for 2 (Figure S4). Notably, the negative θ value could not indicate the antiferromagnetic behavior of 1 and 2 because the depopulation of the upper levels during cooling could also contribute to the negative θ value (-20 K) for Co(II) with octahedral coordination geometry.58 The variable-field magnetization (M) characterizations were

TG and PXRD analyses As shown in Figure S1, compounds 1 and 2 undergo similar multi-step weight loss. The first one for 1 (observed: 8.00%) below 140 °C was due to the loss of free water molecules (cal: 5.00%). There is no significant weight loss from 140 °C to 310 °C. Further heating to about 500 °C leads to the following weight loss (exp: 21.43%) because of the combustion of protonated BAPEN (cal: 24.76%). A short-lived platform appears from 500 °C to 610 °C. Further heating causes the frame to break down. The TG curve of 2 suggests that the first weight loss (exp: 15.82%) below 200°C was due to the loss of free water molecules and coordinated water molecules (cal: 15.26%). A short-lived platform appears from 200 °C to 250 °C. Further heating to about 480 °C leads to the second weight loss (exp: 20.30%) because of the combustion of



Figure 2. (a) Coordination modes of Co ions in 2. (b) The 16-MR building units. (c) 2D layer of 2 composed of 16-MR (organoamines omitted for clarity). (d) The packing structural modes of 2.

investigated in the range 0–5 T at 2 K (Figure 3b). The plots of M vs H show a quasi-linear increase with the increasing fields. For 1, the M value is 2.13 Nβ at 2 K and 5 T, lower than the calculated one of 3.00 Nβ for one Co(II) with g = 2 and S = 3/2 (agreeing with the value of 2.17 Nβ calculated for one Co(II) with gav = 13/3 and Seff = 1/2 per Co (II) at 2K).58 For 2, the M value is 4.30 Nβ at 2K and 5T, smaller than the calculated one of 6.00 Nβ for two Co(II) with g = 2 and S = 3/2 (agreeing with the value of 4.33 Nβ calculated for two Co(II) with gav = 13/3 and Seff = 1/2 per Co (II) at 2K).58 All these information (the shape of the χMT-T and M-H plots and M value at 5 T and 2 K) indicate that compounds 1 and 2 exhibit weak magnetic interaction. Notably, the S-shape of M vs. H plot of 1 implies the potential metamagnetism. The first derivative of M vs. H (dM/dH vs. H) indicates the critical filed is about 27500 Oe (or 2.75 T), which is further testified by the field-dependent magnetic susceptibility (Figure S5). To further investigate the magnetic dynamics of 1 and 2, the frequencyand temperature-dependent ac susceptibilities were studied under a zero direct current field and a 5 Oe ac magnetic field (Figure S6, S7). There are no evident variable-frequency ac signal below 20 K for 1 and 2. The protonated organoamine (H4-BAPEN) in 1 and 2 can serve as proton carriers. For 1, H4-BAPEN form H-bond with the diphosphonate oxygen, and the guest water form H-bond

with hydroxyl oxygen of diphosphonate (Table S3). For 2, H4BAPEN form H-bond with the diphosphonate oxygen and the guest water (Table S4), and H-bond are also observable between the guest water. The H-bond for guest-guest and hostguest are important for proton conduction.55 Thus, proton conduction of compound 1 and 2 have been investigated by alternating current (AC) impedance spectroscopy. 1 and 2 nearly have no conductivity at ambient condition, which may be due to the lack of efficient path for proton conduction.55 When disposing them in closed chamber containing saturated water vapor for 3 days, the conductivity becomes to 8.49 × 105 and 1.93 × 10-5 S cm-1. The impedance as a function of temperature of 1 and 2 have been measured (Figure 3c, d). The conductivity increases with the elevating temperature and reaches 3.57 × 10-4 and 9.43 × 10-5 S cm-1 at 65°C for 1 and 2, respectively. This temperature-dependent property indicates 1 and 2 can be candidates as temperature sensor. Notably, the difference of conductivity between 1 and 2 may be attributed to the difference of crystal structure and hydrogen bonding network. This inspires us to design and regulate topology of the hydrogen bonding network within the metal-phosphonates through crystal engineering. After proton-conducting characterizations, the PXRD patterns of 1 and 2 agree with the simulated ones (Figure S8, S9), proving the structural stability during the process of measurement.


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Figure 3. The curves of χMT vs. T (a) and M vs. H (b) for 1 and 2; The variable-temperature Nyquist plots for 1 (c) and 2 (d) with 100% relative humidity.

Conclusion

AUTHOR INFORMATION

Two cobalt-diphosphonates supported by protonated 1,2bis(3-aminopropylamino)ethane (BAPEN) were prepared and studied. Anionic 1D chain and 2D layer structure are observed in compounds 1 and 2, respectively, and the structural modulation from 1D chain to 2D layer was realized by tuning the synthetic parameters. Systematic research and use of longchain flexible organoamines acting as templates in this family, to the best of knowledge, are still in its fancy. Their magnetism and proton conduction are investigated. Magnetic measurements indicated that the intrachain and intralayer Co(II) ions for 1 and 2 features weak antiferromagnetic coupling. Compounds 1 and 2 show a proton conductivity of 3.57 × 10-4 and 9.43 × 10-5 S cm−1 at 100% RH and 65 °C, respectively. This work highlights the template role of long aliphatic amine in the synthesis of metal-phosphonates. Expanding this synthetic method to other metal-phosphonates is underway, aiming at synthesizing novel crystalline metalphosphonates materials.

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

ORCID Guo-Ming Wang: 0000-0003-0156-904X.

Notes The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS This work was supported by the Natural Science Foundation of China (21571111, 21601101, 21601099).

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ASSOCIATED CONTENT Supporting Information. X-ray crystallographic data file in CIF format for compounds 1 and 2, TG characterizations (Figure S1), PXRD characterizations (Figure S2, S3, S8, S9), Magnetic characterizations (Figure S4-S7), IR plots (Figure S10), selected bond distances and angles (Table S1, S2), and selected H-bond (Table S3, S4). These materials are available free of charge via the Internet at http://pubs.acs.org.



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Rev. 2009, 38 (5), 1353-1379.



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Two cobalt-diphosphonates templated by long-chain flexible amines: synthesis, structures, proton conductivity and magnetic properties Yu-Juan Ma, Song-De Han, Ying Mu, Jie Pan, Jin-Hua Li, and Guo-Ming Wang*

We report two cobalt-diphosphonates templated by protonated 1,2-bis(3-aminopropylamino)ethane. The structure diversities from 1D chain to 2D layer was achieved by adjusting the synthetic parameters. Their magnetism and proton conduction are investigated.


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Two Cobalt-diphosphonates Templated by Long-Chain Flexible Amines

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