- Email: [email protected]
Solvothermal synthesis, structure and properties of heterometallic coordination polymer based on metalloligand and alkaline-earth metal calcium
Journal of Molecular Structure 1186 (2019) 434e439
Contents lists available at ScienceDirect
Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Solvothermal synthesis, structure and properties of heterometallic coordination polymer based on metalloligand and alkaline-earth metal calcium Qianying Nie, Jun Qian*, Chi Zhang** School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013, PR China
a r t i c l e i n f o
a b s t r a c t
Article history: Received 6 January 2019 Received in revised form 12 March 2019 Accepted 15 March 2019 Available online 19 March 2019
A new 3D heterometallic coordination polymer (HCP), which formulated as {[Ca(H2O)2][LCo]$ DMSO$2H2O}n (1) (DMSO ¼ dimethyl sulfoxide), has been solvothermally synthesized from metalloligand LCo ¼ [Co(2,4-pydca)2]2e (2,4-pydca ¼ pyridine-2,4-dicarboxylate) and alkaline-earth ion CaII. HCP 1 has been well characterized by Fourier-transform infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. The crystallographic analysis indicates that HCP 1 crystallizes in the monoclinic system with space group of C2 and possesses the 3D framework structure, which is constructed from metalloligands LCo connecting with CaII ions via the carboxyl groups. The 3D framework of HCP 1 can be defined as (4,4,4)-connected 3-nodal topology with the point symbol of {42$84}{42$84} {42$84}. Thermogravimetric analysis exhibits that the skeleton of HCP 1 collapses after 375 C. Magnetic susceptibility study reveals the presence of antiferromagnetic interaction between the spin centers. The solid-state luminescence property of HCP 1 has also been investigated. © 2019 Elsevier B.V. All rights reserved.
Keywords: Heterometallic coordination polymer Metalloligand Crystal structure Alkaline-earth ion Magnetic property
1. Introduction Nowadays, heterometallic coordination polymers (HCPs) have attracted considerable attention on account of their structure diversities and potential applications in chemical and material science, such as catalysis, magnetism, photoluminescence, and so on [1e4]. It is well known that the rational molecular design of HCPs from different metal centers and ligands is crucial to the molecular configurations and functional properties [5e9]. Recently, the application of metalloligands, which can connect with other metal centers, has been developed to an efficient strategy for the construction of HCPs [10e16]. For instance, molecular building units [MS4]2 (M ¼ W, Mo) and [M(CN)8]3/4 (M ¼ W, Mo, Nb) have been successfully applied as metalloligands in the construction of HCPs with non-linear optical and magnetic properties, respectively [17e20]. In recent years, several heterometallic coordination compounds have been obtained from the new-developed O-containing metalloligand [Cu(2,4-pydca)2] (LCu) [21], which is based on
* Corresponding author. ** Corresponding author. E-mail addresses: [email protected] (J. Qian), [email protected] (C. Zhang). https://doi.org/10.1016/j.molstruc.2019.03.045 0022-2860/© 2019 Elsevier B.V. All rights reserved.
pyridine-2,4-dicarboxylate (2,4-pydca), reacting with transition metal (MnII, CoII, NiII) [22e27] and alkaline-earth ions [28]. To extend the HCPs containing 2,4-pydca based metalloligand, transition metals CoII, NiII, and MnII can also be invited as the metal centers of such kind of metalloligand. (see Scheme 1) On the other hand, the molecular structures and properties of HCPs are also highly influenced by several critical factors during the synthetic process, such as pH values, solvent polarity, metaleligand ratio and synthetic strategy. For example, although several HCPs containing LCu structure have been reported [29e32], in which the LCu come from the reactions between cupric oxide/cupric nitrate and pyridine-2,4-dicarboxylic acid via the hydro-thermal reaction. However, the direct application of metalloligand based on ligand 2,4-pydca in the construction of HCPs is still rare [33]. In addition, compared with transition metal ions, alkaline-earth ions are rare used as metal centers in the construction of coordination compounds due to the fact of that the alkaline-earth ions are hard to be coordinated [34,35]. Meanwhile, benefited from the large spin value, spineion anisotropy and large spin-orbit coupling of CoII ion, compounds containing CoII ion often exhibit fascinating and complicated magnetic behaviors [36,37]. Considering the abovementioned, metalloligand [Co(2,4-pydca)2] (LCo) and alkalineearth ion (CaII) will be introduced for the construction of HCP
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439
435
obtained as orange solid. Yield: of 85% based on Co.
2.3. Synthesis of {[Ca(H2O)2][LCo]·DMSO·2H2O}n (1)
Scheme 1. Structure of metalloligand LCo.
with magnetic properties through the hydro-thermal method. In this paper, we have successfully constructed a 3D structural CaIIeCoII HCP {[Ca(H2O)2][LCo]$DMSO$2H2O}n from metalloligand LCo and alkaline-earth ion CaII with the solvothermal synthetic method. X-ray diffraction analysis reveals that HCP 1 contains gridlike channels through the 3D framework structure, which can be simplified into a (4,4,4)-connected 3-nodal topology. Thermogravimetric analysis exhibits that the skeleton of HCP 1 collapses after 375 C. Magnetic susceptibility study reveals the presence of antiferromagnetic interaction between the spin centers. Moreover, the solid-state luminescence property of HCP 1 has also been investigated. 2. Experimental section 2.1. Materials and physical measurements All chemicals were obtained from commercial sources and directly used without purification. All liquid reagents were soaked with 4 Å molecular sieve before use in order to remove of water. Fourier transform infrared (FT-IR) spectra was obtained at room temperature with a Nicolet Nexus 470 spectrometer and the data was collected in the range of 4000e400 cm1 with dried KBr pellets. Elemental analyses for C, H, and N were performed on a PerkinElmer 240C system. Steady-state fluorescence spectroscopy was used to analyze the luminescence property of the samples and was measured using a PTIQM 40 fluorescence spectrophotometer measurement wavelength range 240e850 nm. Thermogravimetric analysis (TGA) measurements were carried out in the temperature range of 25e800 C on a PerkineElmer Pyis 1 system in a nitrogen purge with a heating rate of 10 C/min. The temperature dependence of molar magnetic susceptibility was measured under an applied field of 1000 G in the form of cmT versus T in the range of 2e300 K by Quantum Design MPMS XL-5. The influence of sample holder background was subtracted by the automatic subtraction feature of the software. 2.2. Synthesis of metalloligand LCo Pyridine-2,4-dicarboxylate (2,4-pydca) was prepared as previously reported method described in the literature [38]. Firstly, pyridine-2, 4-dicarboxylate (20 mmol, 3.3 g) was dissolved into 50 mL distilled water. Afterwards, this solution was gradually drop into an aqueous solution (20 mL) of CoCl2$2H2O (15 mmol, 2.5 g). Half an hour later, a lot of orange powder appeared quickly in the reaction bottle after vigorous stirring at room temperature. The obtained orange filter was washed with distilled water and dried in the air. The dried filtration was added into 100 mL N, N-dimethylformamide (DMF) in a 250 mL neat flask, in which triethylamine was slowly added until a clear dark orange solution is formed. Excess acetone was then added to above mixed solution to precipitate the dark orange solid powder, which was subsequently filtered and washed with acetone. 5.23 g metalloligand LCo was
HCP 1 was solvothermally synthesized from metalloligand LCo and alkaline-earth salt Ca(NO3)2$4H2O in DMSO/MeOH/H2O mixed solution. A 6 mL methanol solution of Ca(NO3)2$4H2O (11.8 mg, 0.05 mmol), 6 mL dimethyl sulfoxide solution (DMSO) of LCo (70.0 mg, 0.1 mmol) and 3 mL MeOH/H2O mixed solution (V:V ¼ 1:1) was sealed in a 23 mL Teflon-lined reactor, which was heated at 120 C in an oven for 24 h, and subsequently cooled to room temperature at a rate of 3 C/h. After that, the cooled solution was placed in the dark with no touch. A week later, 23.3 mg orange prismatic crystals were acquired by filtration, washed with cold MeOH and dried in air. Yield: 40% based on Co. Anal. Calcd for C16H20CaCoN2O13S (579.41): C, 33.14; H, 3.45; N, 4.83. Practical found: C, 33.32; H, 3.42; N, 4.90. IR (KBr, cm1): 3566(m), 1638(s), 1366(s), 1242(m), 1008(m), 697(s).
2.4. X-ray crystallographic studies Crystal of HCP 1 suitable for single crystal X-ray diffraction was obtained directly from above preparation and mounted on a glass fiber with epoxy resin covered to anti-oxidation. The measurement on HCP 1 was performed on Rigaku Saturn 724þ CCD imaging plate diffractometer with graphite-monochromated Mo-Ka radiation (€ e ¼ 0.71073 Å). Cell parameters were refined on all observed reflections by using the program Crystalclear (Rigaku Inc., 2007). The collected data were reduced by the program CrystalClear and an absorption correction (multiscan) was applied using the SADABS program [39]. The reflection data for HCP 1 was also corrected for Lorentz and polarization effects. The crystal structure of HCP 1 were solved by direct methods and refined on F2 by full-matrix leastsquares methods using the SHELXTL software package [40]. All the non-hydrogen atoms were determined with anisotropic thermal displacement coefficients. Detailed crystallographic data of HCP 1 is summarized in Table 1, while the selected bond lengths and angles are listed in Table 2.
Table 1 Crystallographic data and structure refinements for 1. Empirical formula Formula weight Temperature (K) Wavelength (Å) Crystal system Space group a (Å) b (Å) c (Å) a ( ) b ( ) g ( ) V (Å3) Z rcalc (g cm3) m (mm1) F (000) Reflections collected Unique reflections Rint No. parameters GOF R1 [I > 2s(I)] wR2 [I > 2s(I)] Drmax/Drmin (e Å3)
C16H20CaCoN2O13S 579.41 293(2) 0.71073 monoclinic C2 14.666(3) 11.141(2) 7.7126(15) 90 97.77(3) 90 1248.6(4) 2 1.541 1.040 594 5731 2380 0.0367 161 1.231 0.0457 0.1320 1.123 and 0.432
436
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439
Table 2 Selected bond lengths (Å) and angles ( ) for 1. Co(1)-O(3)#1 Co(1)-O(1) Co(1)-N(1)#1 Ca(1)-O(5)#4 Ca(1)-O(6) Ca(1)-O(3)#5 Ca(1)-O(2)#1 Ca(1)-C(1)#5 Ca(1)-H(6A) O(1)-C(7) O(2)-Ca(1)#6 O(3)-C(1) O(3)-Co(1)#6 O(5)-C(7) O(6)-H(6A) N(1)-C(4) S(1)-C(8)
2.060(3) 2.097(4) 2.140(5) 2.331(4) 2.361(5) 2.379(3) 2.947(5) 3.009(6) 2.744(2) 1.283(8) 2.947(5) 1.256(7) 2.060(3) 1.237(8) 0.820(0) 1.325(8) 1.727(1)
O(3)#1-Co(1)-O(3)#2 O(3)#1-Co(1)-O(1) O(3)#1-Co(1)-O(1)#3 O(1)-Co(1)-O(1)#3 O(1)-Co(1)-N(1)#1 O(1)#3-Co(1)-N(1)#1 O(6)-Ca(1)-O(3)#5 O(6)-Ca(1)-O(6)#4 O(6)-Ca(1)-C(1)#5 O(6)#4-Ca(1)-H(6A) C(7)-O(1)-Co(1) Co(1)#6-O(3)-Ca(1)#6 C(7)-O(5)-Ca(1) C(5)-C(1)-Ca(1)#6 O(7)-S(1)-O(7)#7 C(8)-S(1)-C(8)#7 S(1)-C(8)-H(8B)
162.43(2) 102.11(1) 90.50(2) 88.6(2) 174.19(2) 85.58(2) 79.18(1) 100.1(2) 82.14(2) 113.5(1) 124.0(4) 128.52(2) 148.2(4) 160.7(4) 157.6(1) 98.4(8) 109.5(1)
Symmetry transformations used to generate equivalent atoms: #1 xþ1/2,yþ1/2,z #2 -x-1/2,yþ1/2,-z #3 -x,y,-z #4 -x,y,-zþ1 #5 -x-1/2,yþ1/2,-zþ1 #6 x-1/2,y-1/2,z #7 -x-1,y,-z.
3. Results and discussion 3.1. Synthetic method It is well known that hydrothermal or solvothermal synthesis is an efficient method for the crystallization of coordination compounds with complicated structures [2]. HCP 1 was successfully synthesized under the solvothermal condition. The reaction of metalloligand LCo and alkaline-earth salt Ca(NO3)2$4H2O in a molar ratio of 2:1 take place in the DMSO/MeOH/H2O (V:V:V ¼ 4:1:1) mixed solution at 120 C lead to the formation of orange crystals in high purity and yield. Compare to the gentle diffusion method at room temperature [28], the present solvothermal reaction affords the special environment for the formation of 3D polymeric framework. 3.2. IR spectrum As shown in Fig. S1, the IR spectrum of HCP 1 was recorded with dried KBr pellet, which was prepared in a ratio of 1e100 (sample vs KBr). HCP 1 shows a broad band around 3566 cm1, which is corresponding to the OeH stretching band of the H2O molecule. The strong absorption peaks at 1638 cm1 and 1242 cm1 in HCP 1 can be assigned to n(C]O) and n(CeO) vibrations of the 2,4-pydca ligand. The absorption peak at 1366 cm1 indicates the presence of -CH3 in HCP 1, while the peak at 1008 cm1 confirms the retention of S]O bond in DMSO [41]. In addition, the strong peak of 697 cm1 in low frequency fingerprint area attributed to benzene ring bending vibration of 2,4-pydca ligand. 3.3. Crystal structure of HCP 1 The crystal structure of HCP 1 was determined by single-crystal X-ray diffraction, which shows that 1 crystallizes in the monoclinic system with space group of C2 and possesses an infinite 3D framework structure with 3-donal (4,4,4)-connected topology. The overall structure of HCP 1 can be viewed as two-dimensional (2D) metalloligand-based layers sustained by [Ca(H2O)2]2þ cations via the carboxylic acid groups (Fig. 2e). As displayed in Fig. 1a, each Ca atom is eight-coordinated by two O atoms of two H2O molecules and six O atoms of four pyridine-2,4dicarboxylate ligands, in which two O atoms from two 2-pyridinedicarboxylates and two O atoms from two 4-pyridine-dicarboxylates, forms a tetragonal anti-prism geometry. The Co atom in HCP
Fig. 1. (a) Coordination environment of Ca atom. (b) Coordination environment of Co atom. (c) Connecting mode of 2,4-pydca ligand.
1 is six-coordinated by two N atoms and two O atoms of two 2pyridine-dicarboxylates, and two O atoms from two 4-pyridinedicarboxylates, exhibits a distorted Octahedron geometry (Fig. 1b). Generally, coordination number of calcium atom varies from four to six or seven, while the eight-coordination mode for calcium atom is rare [28,42,43]. The high eight-coordination mode of calcium atom in this case maybe result from the solvothermal synthesis. The bond lengths of CoeO range from 2.060(3) to 2.097(4) Å. The values of CaeO bond for carboxylic acid oxygen vary from 2.331(4) to 2.379(3) Å, while 2.947(5) Å belongs to the distance between Ca atom and O atom from water molecules. Due to the excellent coordination ability of carboxylic acid oxygen, the 2,4-pydca ligand from LCo metalloligand connects with two Co atoms and two Ca atoms through the 4-connecting mode (Fig. 1c). The metalloligand LCo in HCP 1 has a V-shaped space configuration with the NeCoeN bond angle of 100.2(4) (Fig. 2a). Owing to the V-shaped structure of metalloligand LCo, four CoII ions are alternately bridged by four pyridine-2,4-dicarboxylate ligands to build a square planar ring (Fig. 2c). Such 4-membered rings can further extend to a 2D metalloligand network (Fig. 2b), corresponding to a sql topology structure (Fig. 2d). These 2D networks are further pillared to the 3D framework (Fig. 2e) via the [Ca(H2O)2]2þ cations (Fig. 2f). The packing diagrams showing the 3D extending structure of HCP 1 are displayed in Fig. S2eS4. As in Fig. S4, the grid-like channels through the 3D framework structure can accept the DMSO and H2O solvent molecules [44e46]. The 3D structure of HCP 1 can be simplified as a (4,4,4)-connected 3-nodal topology with the symbol of {42$84}{42$84}{42$84}, which is depicted in Fig. 3. Compare to the previous reported 0D/1D/2D structures based on LCu and alkaline-earth ion [28], the structural differences between HCP 1 and the reported compounds are mainly due to the coordination modes of carboxylic acid group from metalloligand.
3.4. Thermogravimetric analysis Thermal stability of HCP 1 was investigated from room temperature to 800 C in a nitrogen atmosphere with a heating rate of 10 C/min. Thermogravimetric analysis (TGA) curve is shown in Fig. 4, which shows that the weight loss of HCP 1 can be divided into three stages after 80 C. The first weight loss of 6.38% was
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439
437
Fig. 2. (a) V-shaped structure of metalloligand LCo. (b) 2D network built from LCo metalloligands. (c) 4-membered ring structure in HCP 1. (d) sql topology structure of 2D network. (e) 3D framework of HCP 1. (f) [Ca(H2O)2]2þ cation.
of 170e375 C, the third stage of weight loss (13.30%) corresponding one free DMSO molecules (calcd: 13.46%). With the increase of temperature, the skeleton structure of HCP 1 begins to collapse after 375 C. 3.5. Magnetic properties
Fig. 3. Topological structure of HCP 1.
The temperature dependence of magnetic susceptibility is recorded for crystalline samples of HCP 1 at an applied magnetic field of 0.1 T in the temperature range of 1.8e300 K. As in Fig. 5, the cmT value of HCP 1 at room temperature is 3.47 cm3 mol1$K, which is slightly larger than the expected theoretical range of 2.7e3.4 cm3 mol1 K for one spin-only CoII ion with S ¼ 3/2, g ¼ 2, L ¼ 0 [23,47e49]. Upon decreasing the temperature, the cmT value remains unchanged from 300 to 100 K. After that, the cmT value drops slowly upon cooling, a then it decreases abruptly to a minimum value of 2.12 cm3 mol1 K near 2.0 K. This decrease in cmT may originate in the antiferromagnetic interaction between spin centers. The magnetic data in the whole range fitting with the Curiee-Weiss equation gives a Curie constant of
Fig. 4. TGA curves of HCP 1.
observed within the temperature range of 76e122 C, which is corresponding to the loss of two free solvent water molecules (calcd: 6.21%). The second weight loss (6.07%) occurs from 122 C to 170 C, which is in accordance with the decomposition of two coordinated water molecules (calcd: 6.21%). In the temperature range
Fig. 5. Combination plots of the magnetic susceptibility of cmT vs T and temperature dependence of 1/cm vs T at 0.1 T applied magnetic field.
438
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439
Appendix. ASupplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.molstruc.2019.03.045. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] Fig. 6. Field dependence of magnetization (M) vs field (H) plot at 2 K.
[12] [13]
C ¼ 3.51 cm3 mol1 K and negative weiss constant of q ¼ ¡1.84 K. To conform the antiferromagnetic interaction between spin centers, isothermal magnetization experiment of the magnetization versus field for HCPs 1 was performed at 2 K. As in Fig. 6, the magnetization increases gradually to reach a maximum value of Ms ¼ 2.81 mB at 30 kOe. This finding is in good agreement with a collinear antiferromagnetic ground state [50]. 4. Conclusion
[14] [15] [16] [17] [18] [19] [20]
In summary, we have reported the solvothermal synthesis, structure and magnetic property of 3D framework {[Ca(H2O)2] [LCo]$DMSO$2H2O}n (1), in which the alkaline-earth oxides CaII are bridged by LCo metalloligands via the carboxylate groups. The construction of 3D framework for 1 is mainly due to the excellent coordination ability of carboxylic acid and high coordination mode of calcium cation, which maybe result from the solvothermal synthesis. IR spectra indicates that all the oxygen atoms in the carboxylic acid have been coordinated with the metal atoms. Thermal analysis indicates that the skeleton structure of HCP 1 is stable in the air and begins to collapse after 375 C, which is consistent with the crystal structure characterization. Attribute to the antiferromagnetic interaction between CoII (S ¼ 3/2) spin centers, HCP 1 exhibits antiferromagnetic property with the negative weiss constant of q ¼ ¡1.84 K. Additionally, the fluorescence property of HCP 1 has also been investigated. Further work to explore new metalloligand-based HCPs with interesting magnetic and optical properties are currently in progress. Acknowledgements Financial support from the National Natural Science Foundation of China (Grants 50925207, 51172100, 51432006, and 51602130), the Ministry of Science and Technology of China for the International Science Linkages Program (Grants 2009DFA50620 and 2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (Grant IRT13R24), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (Grant B13025), 100 Talents Program of CAS, Jiangsu Innovation Research Team and Natural Science Foundation of the Higher Education Institutions of Jiangsu Province (Grant 16KJD430002) are gratefully acknowledged.
[21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] [43] [44]
W.L. Leong, J.J. Vittal, Chem. Rev. 111 (2011) 688. rey, T. Loiseau, Cryst. Growth Des. 8 (2008) 685. C. Volkringer, J. Marrot, G. Fe Y.H. Su, S.S. Bao, L.M. Zheng, Inorg. Chem. 53 (2014) 6042. Y.C. Zhang, Y. Yang, H. Jiang, J. Phys. Chem. 117 (2013) 13194. F. Wang, X.M. Jing, B. Zheng, G.H. Li, G. Zeng, Q.S. Huo, Y.L. Liu, Cryst. Growth Des. 13 (2013) 3522. T.R. Cook, Y.R. Zheng, P.J. Stang, Chem. Rev. 113 (2013) 734. J.M. Zadrozny, D.J. Xiao, M. Atanasov, G.J. Long, F. Grandjean, F. Neese, J.R. Long, Nat. Chem. 5 (2013) 577. R. Bikas, B. Soltani, H. Sheykhi, M. Korabik, M. Hossaini-Sadr, J. Mol. Struct. 1168 (2018) 195. T. Kido, Y. Ikuta, Y. Sunatsuki, Y. Ogawa, N. Matsumoto, Inorg. Chem. 42 (2003) 398. J.D. Rinehart, M. Fang, W.J. Evans, J.R. Long, Nat. Chem. 3 (2011) 538. M. Masoudi, M. Behzad, A. Arab, A. Tarahhomi, H. Amiri Rudbari, G. Bruno, J. Mol. Struct. 1122 (2016) 123. P. Richardson, K.J. Gagnon, S.J. Teat, G. Lorusso, M. Evangelisti, J.K. Tang, T.C. Stamatatos, Cryst. Growth Des. 17 (2017) 2486. D. Dermitzaki, G. Lorusso, C.P. Raptopoulou, V. Psycharis, V. Escuer, M. Evangelisti, S.P. Perlepes, T.C. Stamatatos, Inorg. Chem. 52 (2013) 10235. G.L. Zhuang, W.X. Chen, H.X. Zhao, X.J. Kong, L.S. Long, R.B. Huang, L.S. Zheng, Inorg. Chem. 50 (2011) 3843. M. Kobayashi, D. Savard, A.R. Geisheimer, K. Sakai, D.B. Leznoff, Inorg. Chem. 52 (2013) 4842. J.B. Peng, Q.C. Zhang, X.J. Kong, Y.Z. Zheng, Y.P. Ren, L.S. Long, R.B. Huang, L.S. Zheng, Z.P. Zheng, J. Am. Chem. Soc. 134 (2012) 3314. J. Qian, J.C. Hu, J.F. Zhang, H. Yoshikawa, K. Awaga, C. Zhang, Cryst. Growth Des. 13 (2013) 5211. K. Qian, X.C. Huang, C. Zhou, X.Z. You, X.Y. Wang, K.R. Dunbar, J. Am. Chem. Soc. 135 (2013) 13302. K. Tomono, Y. Tsunobuchi, K. Nakabayashi, S. Ohkoshi, Inorg. Chem. 49 (2010) 1298. J. Qian, H.J. Zhao, H.Y. Wei, J.H. Li, J.F. Zhang, H. Yoshikawa, K. Awagac, C. Zhang, CrystEngComm 13 (2011) 517. Y.G. Huang, M.Y. Wu, W. Wei, Q. Gao, D.Q. Yuan, F.L. Jiang, M.C. Hong, J. Mol. Struct. 885 (2008) 23. D. Rajan, P.A. Quintero, K.A. Abboud, M.W. Meisel, D.R. Talham, Polyhedron 66 (2013) 142. X.L. Li, F.Y. Min, C. Wang, S.Y. Lin, Z.L. Liu, J.K. Tang, Inorg. Chem. 54 (2015) 4337. G.J. Zhou, W.P. Chen, Y.Z. Yu, L. Qin, T. Han, Y.Z. Zheng, Inorg. Chem. 56 (2017) 12821. Y. Ouyang, W. Zhang, N. Xu, G.F. Xu, D.Z. Liao, K. Yoshimura, S.P. Yan, P. Cheng, Inorg. Chem. 46 (2007) 8454. M.Y. Li, Y.H. Lan, A.M. Ako, W. Wernsdorfer, C.E. Anson, G. Buth, A.K. Powell, Z.M. Wang, S. Gao, Inorg. Chem. 49 (2010) 11587. P. Díaz-Gallifa, O. Fabelo, J. Pas an, L. Caneadillas-Delgado, F. Lloret, M. Julve, rez, Inorg. Chem. 53 (2014) 6299. C. Ruiz-Pe Q. Zhou, J. Qian, C. Zhang, J. Mol. Struct. 1119 (2016) 340. X.F. Li, Y. Huang, R. Cao, Cryst. Growth Des. 12 (2012) 3549. A. Singha, F. Donati, C. Wackerlin, R. Baltic, J. Dreiser, M. Pivetta, S. Rusponi, H. Brune, Nano Lett. 16 (2016) 3475. D. Dermitzaki, C.P. Raptopoulou, V. Psycharis, A. Escuer, S.P. Perlepes, T.C. Stamatatos, Inorg. Chem. 54 (2015) 7555. Y.Z. Tang, H.R. Wen, Z. Cao, X.W. Wang, S. Huang, C.L. Yu, Inorg. Chem. Commun. 13 (2010) 924. Y.C. Liang, R. Cao, M.C. Hong, D.F. Sun, Y.J. Zhao, J.B. Weng, R.H. Wang, Inorg. Chem. Commun. 5 (2002) 366. H.Q. Wu, P. Ju, H. He, B.F. Yang, G.Y. Yang, Inorg. Chem. 52 (2013) 10566. S. Noro, J. Mizutani, Y. Hijikata, R. Matsuda, H. Sato, S. Kitagawa, K. Sugimoto, Y. Inubushi, K. Kubo, T. Nakamura, Nat. Commun. 6 (2015) 5851. J. Goura, A. Chakraborty, J.P.S. Walsh, F. Tuna, V. Chandrasekhar, Cryst. Growth Des. 15 (2015) 3157. V.P. Radha, S. Jone Kirubavathy, S. Chitra, J. Mol. Struct. 1165 (2018) 246. S.I. Noro, H. Miyasaka, S. Kitagawa, T. Wada, T. Okubo, M. Yamashita, T. Mitani, Inorg. Chem. 44 (2005) 133. G.M. Sheldrick, SADABS, Program for Area Detector Adsorption Correction, Institute for Inorganic Chemistry, University of Gottingen, Germany, 1996. G.M. Sheldrick, SHELXL-97, Program for Refinement of Crystal Structures, University of Gottingen, Germany, 1997. T.N. Diao, P. White, I. Guzei, S.S. Stahl, Inorg. Chem. 51 (2012) 11898. P.C. Liang, H.K. Liu, C.T. Yeh, C.H. Lin, V. Zima, Cryst. Growth Des. 11 (2011) 699. J.D. Lin, S.T. Wu, Z.H. Lia, S.W. Du, Dalton Trans. 39 (2010) 10719. Y.F. Han, Z.B. Zheng, C.A. Wang, J.F. Sun, X.Y. Li, J.P. Zhang, J. Xiao, G.F. He, L.Q. Li, J. Mol. Struct. 1079 (2015) 163.
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439 [45] A. Ghaffari, M. Behzad, M. Pooyan, H.A. Rudbari, G. Bruno, J. Mol. Struct. 1063 (2014) 1. [46] Y.G. Huang, Y.F. Zhou, D.Q. Yuan, B.L. Wu, F.L. Jiang, M.C. Hong, J. Mol. Struct. 830 (2007) 85. [47] G.F. Xu, P. Gamez, J.K. Tang, R. Clerac, Y.N. Guo, Y. Guo, Inorg. Chem. 51 (2012) 5693.
439
mez, L. Vendier, M. Corbella, J.P. Costes, Inorg. Chem. 51 (2012) 6396. [48] V. Go [49] J. Lin, K. Diefenbach, M.A. Silver, N.S. Dalal, T.E. Albrecht-Schmitt, Cryst. Growth Des. 15 (2015) 4606. [50] Y.Y. Tang, M.Y. Cui, W.B. Guo, S.Y. Zhang, M. Yang, Z.Z. He, Cryst. Growth Des. 15 (2015) 2742.
Contents lists available at ScienceDirect
Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Solvothermal synthesis, structure and properties of heterometallic coordination polymer based on metalloligand and alkaline-earth metal calcium Qianying Nie, Jun Qian*, Chi Zhang** School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013, PR China
a r t i c l e i n f o
a b s t r a c t
Article history: Received 6 January 2019 Received in revised form 12 March 2019 Accepted 15 March 2019 Available online 19 March 2019
A new 3D heterometallic coordination polymer (HCP), which formulated as {[Ca(H2O)2][LCo]$ DMSO$2H2O}n (1) (DMSO ¼ dimethyl sulfoxide), has been solvothermally synthesized from metalloligand LCo ¼ [Co(2,4-pydca)2]2e (2,4-pydca ¼ pyridine-2,4-dicarboxylate) and alkaline-earth ion CaII. HCP 1 has been well characterized by Fourier-transform infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. The crystallographic analysis indicates that HCP 1 crystallizes in the monoclinic system with space group of C2 and possesses the 3D framework structure, which is constructed from metalloligands LCo connecting with CaII ions via the carboxyl groups. The 3D framework of HCP 1 can be defined as (4,4,4)-connected 3-nodal topology with the point symbol of {42$84}{42$84} {42$84}. Thermogravimetric analysis exhibits that the skeleton of HCP 1 collapses after 375 C. Magnetic susceptibility study reveals the presence of antiferromagnetic interaction between the spin centers. The solid-state luminescence property of HCP 1 has also been investigated. © 2019 Elsevier B.V. All rights reserved.
Keywords: Heterometallic coordination polymer Metalloligand Crystal structure Alkaline-earth ion Magnetic property
1. Introduction Nowadays, heterometallic coordination polymers (HCPs) have attracted considerable attention on account of their structure diversities and potential applications in chemical and material science, such as catalysis, magnetism, photoluminescence, and so on [1e4]. It is well known that the rational molecular design of HCPs from different metal centers and ligands is crucial to the molecular configurations and functional properties [5e9]. Recently, the application of metalloligands, which can connect with other metal centers, has been developed to an efficient strategy for the construction of HCPs [10e16]. For instance, molecular building units [MS4]2 (M ¼ W, Mo) and [M(CN)8]3/4 (M ¼ W, Mo, Nb) have been successfully applied as metalloligands in the construction of HCPs with non-linear optical and magnetic properties, respectively [17e20]. In recent years, several heterometallic coordination compounds have been obtained from the new-developed O-containing metalloligand [Cu(2,4-pydca)2] (LCu) [21], which is based on
* Corresponding author. ** Corresponding author. E-mail addresses: [email protected] (J. Qian), [email protected] (C. Zhang). https://doi.org/10.1016/j.molstruc.2019.03.045 0022-2860/© 2019 Elsevier B.V. All rights reserved.
pyridine-2,4-dicarboxylate (2,4-pydca), reacting with transition metal (MnII, CoII, NiII) [22e27] and alkaline-earth ions [28]. To extend the HCPs containing 2,4-pydca based metalloligand, transition metals CoII, NiII, and MnII can also be invited as the metal centers of such kind of metalloligand. (see Scheme 1) On the other hand, the molecular structures and properties of HCPs are also highly influenced by several critical factors during the synthetic process, such as pH values, solvent polarity, metaleligand ratio and synthetic strategy. For example, although several HCPs containing LCu structure have been reported [29e32], in which the LCu come from the reactions between cupric oxide/cupric nitrate and pyridine-2,4-dicarboxylic acid via the hydro-thermal reaction. However, the direct application of metalloligand based on ligand 2,4-pydca in the construction of HCPs is still rare [33]. In addition, compared with transition metal ions, alkaline-earth ions are rare used as metal centers in the construction of coordination compounds due to the fact of that the alkaline-earth ions are hard to be coordinated [34,35]. Meanwhile, benefited from the large spin value, spineion anisotropy and large spin-orbit coupling of CoII ion, compounds containing CoII ion often exhibit fascinating and complicated magnetic behaviors [36,37]. Considering the abovementioned, metalloligand [Co(2,4-pydca)2] (LCo) and alkalineearth ion (CaII) will be introduced for the construction of HCP
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439
435
obtained as orange solid. Yield: of 85% based on Co.
2.3. Synthesis of {[Ca(H2O)2][LCo]·DMSO·2H2O}n (1)
Scheme 1. Structure of metalloligand LCo.
with magnetic properties through the hydro-thermal method. In this paper, we have successfully constructed a 3D structural CaIIeCoII HCP {[Ca(H2O)2][LCo]$DMSO$2H2O}n from metalloligand LCo and alkaline-earth ion CaII with the solvothermal synthetic method. X-ray diffraction analysis reveals that HCP 1 contains gridlike channels through the 3D framework structure, which can be simplified into a (4,4,4)-connected 3-nodal topology. Thermogravimetric analysis exhibits that the skeleton of HCP 1 collapses after 375 C. Magnetic susceptibility study reveals the presence of antiferromagnetic interaction between the spin centers. Moreover, the solid-state luminescence property of HCP 1 has also been investigated. 2. Experimental section 2.1. Materials and physical measurements All chemicals were obtained from commercial sources and directly used without purification. All liquid reagents were soaked with 4 Å molecular sieve before use in order to remove of water. Fourier transform infrared (FT-IR) spectra was obtained at room temperature with a Nicolet Nexus 470 spectrometer and the data was collected in the range of 4000e400 cm1 with dried KBr pellets. Elemental analyses for C, H, and N were performed on a PerkinElmer 240C system. Steady-state fluorescence spectroscopy was used to analyze the luminescence property of the samples and was measured using a PTIQM 40 fluorescence spectrophotometer measurement wavelength range 240e850 nm. Thermogravimetric analysis (TGA) measurements were carried out in the temperature range of 25e800 C on a PerkineElmer Pyis 1 system in a nitrogen purge with a heating rate of 10 C/min. The temperature dependence of molar magnetic susceptibility was measured under an applied field of 1000 G in the form of cmT versus T in the range of 2e300 K by Quantum Design MPMS XL-5. The influence of sample holder background was subtracted by the automatic subtraction feature of the software. 2.2. Synthesis of metalloligand LCo Pyridine-2,4-dicarboxylate (2,4-pydca) was prepared as previously reported method described in the literature [38]. Firstly, pyridine-2, 4-dicarboxylate (20 mmol, 3.3 g) was dissolved into 50 mL distilled water. Afterwards, this solution was gradually drop into an aqueous solution (20 mL) of CoCl2$2H2O (15 mmol, 2.5 g). Half an hour later, a lot of orange powder appeared quickly in the reaction bottle after vigorous stirring at room temperature. The obtained orange filter was washed with distilled water and dried in the air. The dried filtration was added into 100 mL N, N-dimethylformamide (DMF) in a 250 mL neat flask, in which triethylamine was slowly added until a clear dark orange solution is formed. Excess acetone was then added to above mixed solution to precipitate the dark orange solid powder, which was subsequently filtered and washed with acetone. 5.23 g metalloligand LCo was
HCP 1 was solvothermally synthesized from metalloligand LCo and alkaline-earth salt Ca(NO3)2$4H2O in DMSO/MeOH/H2O mixed solution. A 6 mL methanol solution of Ca(NO3)2$4H2O (11.8 mg, 0.05 mmol), 6 mL dimethyl sulfoxide solution (DMSO) of LCo (70.0 mg, 0.1 mmol) and 3 mL MeOH/H2O mixed solution (V:V ¼ 1:1) was sealed in a 23 mL Teflon-lined reactor, which was heated at 120 C in an oven for 24 h, and subsequently cooled to room temperature at a rate of 3 C/h. After that, the cooled solution was placed in the dark with no touch. A week later, 23.3 mg orange prismatic crystals were acquired by filtration, washed with cold MeOH and dried in air. Yield: 40% based on Co. Anal. Calcd for C16H20CaCoN2O13S (579.41): C, 33.14; H, 3.45; N, 4.83. Practical found: C, 33.32; H, 3.42; N, 4.90. IR (KBr, cm1): 3566(m), 1638(s), 1366(s), 1242(m), 1008(m), 697(s).
2.4. X-ray crystallographic studies Crystal of HCP 1 suitable for single crystal X-ray diffraction was obtained directly from above preparation and mounted on a glass fiber with epoxy resin covered to anti-oxidation. The measurement on HCP 1 was performed on Rigaku Saturn 724þ CCD imaging plate diffractometer with graphite-monochromated Mo-Ka radiation (€ e ¼ 0.71073 Å). Cell parameters were refined on all observed reflections by using the program Crystalclear (Rigaku Inc., 2007). The collected data were reduced by the program CrystalClear and an absorption correction (multiscan) was applied using the SADABS program [39]. The reflection data for HCP 1 was also corrected for Lorentz and polarization effects. The crystal structure of HCP 1 were solved by direct methods and refined on F2 by full-matrix leastsquares methods using the SHELXTL software package [40]. All the non-hydrogen atoms were determined with anisotropic thermal displacement coefficients. Detailed crystallographic data of HCP 1 is summarized in Table 1, while the selected bond lengths and angles are listed in Table 2.
Table 1 Crystallographic data and structure refinements for 1. Empirical formula Formula weight Temperature (K) Wavelength (Å) Crystal system Space group a (Å) b (Å) c (Å) a ( ) b ( ) g ( ) V (Å3) Z rcalc (g cm3) m (mm1) F (000) Reflections collected Unique reflections Rint No. parameters GOF R1 [I > 2s(I)] wR2 [I > 2s(I)] Drmax/Drmin (e Å3)
C16H20CaCoN2O13S 579.41 293(2) 0.71073 monoclinic C2 14.666(3) 11.141(2) 7.7126(15) 90 97.77(3) 90 1248.6(4) 2 1.541 1.040 594 5731 2380 0.0367 161 1.231 0.0457 0.1320 1.123 and 0.432
436
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439
Table 2 Selected bond lengths (Å) and angles ( ) for 1. Co(1)-O(3)#1 Co(1)-O(1) Co(1)-N(1)#1 Ca(1)-O(5)#4 Ca(1)-O(6) Ca(1)-O(3)#5 Ca(1)-O(2)#1 Ca(1)-C(1)#5 Ca(1)-H(6A) O(1)-C(7) O(2)-Ca(1)#6 O(3)-C(1) O(3)-Co(1)#6 O(5)-C(7) O(6)-H(6A) N(1)-C(4) S(1)-C(8)
2.060(3) 2.097(4) 2.140(5) 2.331(4) 2.361(5) 2.379(3) 2.947(5) 3.009(6) 2.744(2) 1.283(8) 2.947(5) 1.256(7) 2.060(3) 1.237(8) 0.820(0) 1.325(8) 1.727(1)
O(3)#1-Co(1)-O(3)#2 O(3)#1-Co(1)-O(1) O(3)#1-Co(1)-O(1)#3 O(1)-Co(1)-O(1)#3 O(1)-Co(1)-N(1)#1 O(1)#3-Co(1)-N(1)#1 O(6)-Ca(1)-O(3)#5 O(6)-Ca(1)-O(6)#4 O(6)-Ca(1)-C(1)#5 O(6)#4-Ca(1)-H(6A) C(7)-O(1)-Co(1) Co(1)#6-O(3)-Ca(1)#6 C(7)-O(5)-Ca(1) C(5)-C(1)-Ca(1)#6 O(7)-S(1)-O(7)#7 C(8)-S(1)-C(8)#7 S(1)-C(8)-H(8B)
162.43(2) 102.11(1) 90.50(2) 88.6(2) 174.19(2) 85.58(2) 79.18(1) 100.1(2) 82.14(2) 113.5(1) 124.0(4) 128.52(2) 148.2(4) 160.7(4) 157.6(1) 98.4(8) 109.5(1)
Symmetry transformations used to generate equivalent atoms: #1 xþ1/2,yþ1/2,z #2 -x-1/2,yþ1/2,-z #3 -x,y,-z #4 -x,y,-zþ1 #5 -x-1/2,yþ1/2,-zþ1 #6 x-1/2,y-1/2,z #7 -x-1,y,-z.
3. Results and discussion 3.1. Synthetic method It is well known that hydrothermal or solvothermal synthesis is an efficient method for the crystallization of coordination compounds with complicated structures [2]. HCP 1 was successfully synthesized under the solvothermal condition. The reaction of metalloligand LCo and alkaline-earth salt Ca(NO3)2$4H2O in a molar ratio of 2:1 take place in the DMSO/MeOH/H2O (V:V:V ¼ 4:1:1) mixed solution at 120 C lead to the formation of orange crystals in high purity and yield. Compare to the gentle diffusion method at room temperature [28], the present solvothermal reaction affords the special environment for the formation of 3D polymeric framework. 3.2. IR spectrum As shown in Fig. S1, the IR spectrum of HCP 1 was recorded with dried KBr pellet, which was prepared in a ratio of 1e100 (sample vs KBr). HCP 1 shows a broad band around 3566 cm1, which is corresponding to the OeH stretching band of the H2O molecule. The strong absorption peaks at 1638 cm1 and 1242 cm1 in HCP 1 can be assigned to n(C]O) and n(CeO) vibrations of the 2,4-pydca ligand. The absorption peak at 1366 cm1 indicates the presence of -CH3 in HCP 1, while the peak at 1008 cm1 confirms the retention of S]O bond in DMSO [41]. In addition, the strong peak of 697 cm1 in low frequency fingerprint area attributed to benzene ring bending vibration of 2,4-pydca ligand. 3.3. Crystal structure of HCP 1 The crystal structure of HCP 1 was determined by single-crystal X-ray diffraction, which shows that 1 crystallizes in the monoclinic system with space group of C2 and possesses an infinite 3D framework structure with 3-donal (4,4,4)-connected topology. The overall structure of HCP 1 can be viewed as two-dimensional (2D) metalloligand-based layers sustained by [Ca(H2O)2]2þ cations via the carboxylic acid groups (Fig. 2e). As displayed in Fig. 1a, each Ca atom is eight-coordinated by two O atoms of two H2O molecules and six O atoms of four pyridine-2,4dicarboxylate ligands, in which two O atoms from two 2-pyridinedicarboxylates and two O atoms from two 4-pyridine-dicarboxylates, forms a tetragonal anti-prism geometry. The Co atom in HCP
Fig. 1. (a) Coordination environment of Ca atom. (b) Coordination environment of Co atom. (c) Connecting mode of 2,4-pydca ligand.
1 is six-coordinated by two N atoms and two O atoms of two 2pyridine-dicarboxylates, and two O atoms from two 4-pyridinedicarboxylates, exhibits a distorted Octahedron geometry (Fig. 1b). Generally, coordination number of calcium atom varies from four to six or seven, while the eight-coordination mode for calcium atom is rare [28,42,43]. The high eight-coordination mode of calcium atom in this case maybe result from the solvothermal synthesis. The bond lengths of CoeO range from 2.060(3) to 2.097(4) Å. The values of CaeO bond for carboxylic acid oxygen vary from 2.331(4) to 2.379(3) Å, while 2.947(5) Å belongs to the distance between Ca atom and O atom from water molecules. Due to the excellent coordination ability of carboxylic acid oxygen, the 2,4-pydca ligand from LCo metalloligand connects with two Co atoms and two Ca atoms through the 4-connecting mode (Fig. 1c). The metalloligand LCo in HCP 1 has a V-shaped space configuration with the NeCoeN bond angle of 100.2(4) (Fig. 2a). Owing to the V-shaped structure of metalloligand LCo, four CoII ions are alternately bridged by four pyridine-2,4-dicarboxylate ligands to build a square planar ring (Fig. 2c). Such 4-membered rings can further extend to a 2D metalloligand network (Fig. 2b), corresponding to a sql topology structure (Fig. 2d). These 2D networks are further pillared to the 3D framework (Fig. 2e) via the [Ca(H2O)2]2þ cations (Fig. 2f). The packing diagrams showing the 3D extending structure of HCP 1 are displayed in Fig. S2eS4. As in Fig. S4, the grid-like channels through the 3D framework structure can accept the DMSO and H2O solvent molecules [44e46]. The 3D structure of HCP 1 can be simplified as a (4,4,4)-connected 3-nodal topology with the symbol of {42$84}{42$84}{42$84}, which is depicted in Fig. 3. Compare to the previous reported 0D/1D/2D structures based on LCu and alkaline-earth ion [28], the structural differences between HCP 1 and the reported compounds are mainly due to the coordination modes of carboxylic acid group from metalloligand.
3.4. Thermogravimetric analysis Thermal stability of HCP 1 was investigated from room temperature to 800 C in a nitrogen atmosphere with a heating rate of 10 C/min. Thermogravimetric analysis (TGA) curve is shown in Fig. 4, which shows that the weight loss of HCP 1 can be divided into three stages after 80 C. The first weight loss of 6.38% was
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439
437
Fig. 2. (a) V-shaped structure of metalloligand LCo. (b) 2D network built from LCo metalloligands. (c) 4-membered ring structure in HCP 1. (d) sql topology structure of 2D network. (e) 3D framework of HCP 1. (f) [Ca(H2O)2]2þ cation.
of 170e375 C, the third stage of weight loss (13.30%) corresponding one free DMSO molecules (calcd: 13.46%). With the increase of temperature, the skeleton structure of HCP 1 begins to collapse after 375 C. 3.5. Magnetic properties
Fig. 3. Topological structure of HCP 1.
The temperature dependence of magnetic susceptibility is recorded for crystalline samples of HCP 1 at an applied magnetic field of 0.1 T in the temperature range of 1.8e300 K. As in Fig. 5, the cmT value of HCP 1 at room temperature is 3.47 cm3 mol1$K, which is slightly larger than the expected theoretical range of 2.7e3.4 cm3 mol1 K for one spin-only CoII ion with S ¼ 3/2, g ¼ 2, L ¼ 0 [23,47e49]. Upon decreasing the temperature, the cmT value remains unchanged from 300 to 100 K. After that, the cmT value drops slowly upon cooling, a then it decreases abruptly to a minimum value of 2.12 cm3 mol1 K near 2.0 K. This decrease in cmT may originate in the antiferromagnetic interaction between spin centers. The magnetic data in the whole range fitting with the Curiee-Weiss equation gives a Curie constant of
Fig. 4. TGA curves of HCP 1.
observed within the temperature range of 76e122 C, which is corresponding to the loss of two free solvent water molecules (calcd: 6.21%). The second weight loss (6.07%) occurs from 122 C to 170 C, which is in accordance with the decomposition of two coordinated water molecules (calcd: 6.21%). In the temperature range
Fig. 5. Combination plots of the magnetic susceptibility of cmT vs T and temperature dependence of 1/cm vs T at 0.1 T applied magnetic field.
438
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439
Appendix. ASupplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.molstruc.2019.03.045. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] Fig. 6. Field dependence of magnetization (M) vs field (H) plot at 2 K.
[12] [13]
C ¼ 3.51 cm3 mol1 K and negative weiss constant of q ¼ ¡1.84 K. To conform the antiferromagnetic interaction between spin centers, isothermal magnetization experiment of the magnetization versus field for HCPs 1 was performed at 2 K. As in Fig. 6, the magnetization increases gradually to reach a maximum value of Ms ¼ 2.81 mB at 30 kOe. This finding is in good agreement with a collinear antiferromagnetic ground state [50]. 4. Conclusion
[14] [15] [16] [17] [18] [19] [20]
In summary, we have reported the solvothermal synthesis, structure and magnetic property of 3D framework {[Ca(H2O)2] [LCo]$DMSO$2H2O}n (1), in which the alkaline-earth oxides CaII are bridged by LCo metalloligands via the carboxylate groups. The construction of 3D framework for 1 is mainly due to the excellent coordination ability of carboxylic acid and high coordination mode of calcium cation, which maybe result from the solvothermal synthesis. IR spectra indicates that all the oxygen atoms in the carboxylic acid have been coordinated with the metal atoms. Thermal analysis indicates that the skeleton structure of HCP 1 is stable in the air and begins to collapse after 375 C, which is consistent with the crystal structure characterization. Attribute to the antiferromagnetic interaction between CoII (S ¼ 3/2) spin centers, HCP 1 exhibits antiferromagnetic property with the negative weiss constant of q ¼ ¡1.84 K. Additionally, the fluorescence property of HCP 1 has also been investigated. Further work to explore new metalloligand-based HCPs with interesting magnetic and optical properties are currently in progress. Acknowledgements Financial support from the National Natural Science Foundation of China (Grants 50925207, 51172100, 51432006, and 51602130), the Ministry of Science and Technology of China for the International Science Linkages Program (Grants 2009DFA50620 and 2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (Grant IRT13R24), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (Grant B13025), 100 Talents Program of CAS, Jiangsu Innovation Research Team and Natural Science Foundation of the Higher Education Institutions of Jiangsu Province (Grant 16KJD430002) are gratefully acknowledged.
[21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] [43] [44]
W.L. Leong, J.J. Vittal, Chem. Rev. 111 (2011) 688. rey, T. Loiseau, Cryst. Growth Des. 8 (2008) 685. C. Volkringer, J. Marrot, G. Fe Y.H. Su, S.S. Bao, L.M. Zheng, Inorg. Chem. 53 (2014) 6042. Y.C. Zhang, Y. Yang, H. Jiang, J. Phys. Chem. 117 (2013) 13194. F. Wang, X.M. Jing, B. Zheng, G.H. Li, G. Zeng, Q.S. Huo, Y.L. Liu, Cryst. Growth Des. 13 (2013) 3522. T.R. Cook, Y.R. Zheng, P.J. Stang, Chem. Rev. 113 (2013) 734. J.M. Zadrozny, D.J. Xiao, M. Atanasov, G.J. Long, F. Grandjean, F. Neese, J.R. Long, Nat. Chem. 5 (2013) 577. R. Bikas, B. Soltani, H. Sheykhi, M. Korabik, M. Hossaini-Sadr, J. Mol. Struct. 1168 (2018) 195. T. Kido, Y. Ikuta, Y. Sunatsuki, Y. Ogawa, N. Matsumoto, Inorg. Chem. 42 (2003) 398. J.D. Rinehart, M. Fang, W.J. Evans, J.R. Long, Nat. Chem. 3 (2011) 538. M. Masoudi, M. Behzad, A. Arab, A. Tarahhomi, H. Amiri Rudbari, G. Bruno, J. Mol. Struct. 1122 (2016) 123. P. Richardson, K.J. Gagnon, S.J. Teat, G. Lorusso, M. Evangelisti, J.K. Tang, T.C. Stamatatos, Cryst. Growth Des. 17 (2017) 2486. D. Dermitzaki, G. Lorusso, C.P. Raptopoulou, V. Psycharis, V. Escuer, M. Evangelisti, S.P. Perlepes, T.C. Stamatatos, Inorg. Chem. 52 (2013) 10235. G.L. Zhuang, W.X. Chen, H.X. Zhao, X.J. Kong, L.S. Long, R.B. Huang, L.S. Zheng, Inorg. Chem. 50 (2011) 3843. M. Kobayashi, D. Savard, A.R. Geisheimer, K. Sakai, D.B. Leznoff, Inorg. Chem. 52 (2013) 4842. J.B. Peng, Q.C. Zhang, X.J. Kong, Y.Z. Zheng, Y.P. Ren, L.S. Long, R.B. Huang, L.S. Zheng, Z.P. Zheng, J. Am. Chem. Soc. 134 (2012) 3314. J. Qian, J.C. Hu, J.F. Zhang, H. Yoshikawa, K. Awaga, C. Zhang, Cryst. Growth Des. 13 (2013) 5211. K. Qian, X.C. Huang, C. Zhou, X.Z. You, X.Y. Wang, K.R. Dunbar, J. Am. Chem. Soc. 135 (2013) 13302. K. Tomono, Y. Tsunobuchi, K. Nakabayashi, S. Ohkoshi, Inorg. Chem. 49 (2010) 1298. J. Qian, H.J. Zhao, H.Y. Wei, J.H. Li, J.F. Zhang, H. Yoshikawa, K. Awagac, C. Zhang, CrystEngComm 13 (2011) 517. Y.G. Huang, M.Y. Wu, W. Wei, Q. Gao, D.Q. Yuan, F.L. Jiang, M.C. Hong, J. Mol. Struct. 885 (2008) 23. D. Rajan, P.A. Quintero, K.A. Abboud, M.W. Meisel, D.R. Talham, Polyhedron 66 (2013) 142. X.L. Li, F.Y. Min, C. Wang, S.Y. Lin, Z.L. Liu, J.K. Tang, Inorg. Chem. 54 (2015) 4337. G.J. Zhou, W.P. Chen, Y.Z. Yu, L. Qin, T. Han, Y.Z. Zheng, Inorg. Chem. 56 (2017) 12821. Y. Ouyang, W. Zhang, N. Xu, G.F. Xu, D.Z. Liao, K. Yoshimura, S.P. Yan, P. Cheng, Inorg. Chem. 46 (2007) 8454. M.Y. Li, Y.H. Lan, A.M. Ako, W. Wernsdorfer, C.E. Anson, G. Buth, A.K. Powell, Z.M. Wang, S. Gao, Inorg. Chem. 49 (2010) 11587. P. Díaz-Gallifa, O. Fabelo, J. Pas an, L. Caneadillas-Delgado, F. Lloret, M. Julve, rez, Inorg. Chem. 53 (2014) 6299. C. Ruiz-Pe Q. Zhou, J. Qian, C. Zhang, J. Mol. Struct. 1119 (2016) 340. X.F. Li, Y. Huang, R. Cao, Cryst. Growth Des. 12 (2012) 3549. A. Singha, F. Donati, C. Wackerlin, R. Baltic, J. Dreiser, M. Pivetta, S. Rusponi, H. Brune, Nano Lett. 16 (2016) 3475. D. Dermitzaki, C.P. Raptopoulou, V. Psycharis, A. Escuer, S.P. Perlepes, T.C. Stamatatos, Inorg. Chem. 54 (2015) 7555. Y.Z. Tang, H.R. Wen, Z. Cao, X.W. Wang, S. Huang, C.L. Yu, Inorg. Chem. Commun. 13 (2010) 924. Y.C. Liang, R. Cao, M.C. Hong, D.F. Sun, Y.J. Zhao, J.B. Weng, R.H. Wang, Inorg. Chem. Commun. 5 (2002) 366. H.Q. Wu, P. Ju, H. He, B.F. Yang, G.Y. Yang, Inorg. Chem. 52 (2013) 10566. S. Noro, J. Mizutani, Y. Hijikata, R. Matsuda, H. Sato, S. Kitagawa, K. Sugimoto, Y. Inubushi, K. Kubo, T. Nakamura, Nat. Commun. 6 (2015) 5851. J. Goura, A. Chakraborty, J.P.S. Walsh, F. Tuna, V. Chandrasekhar, Cryst. Growth Des. 15 (2015) 3157. V.P. Radha, S. Jone Kirubavathy, S. Chitra, J. Mol. Struct. 1165 (2018) 246. S.I. Noro, H. Miyasaka, S. Kitagawa, T. Wada, T. Okubo, M. Yamashita, T. Mitani, Inorg. Chem. 44 (2005) 133. G.M. Sheldrick, SADABS, Program for Area Detector Adsorption Correction, Institute for Inorganic Chemistry, University of Gottingen, Germany, 1996. G.M. Sheldrick, SHELXL-97, Program for Refinement of Crystal Structures, University of Gottingen, Germany, 1997. T.N. Diao, P. White, I. Guzei, S.S. Stahl, Inorg. Chem. 51 (2012) 11898. P.C. Liang, H.K. Liu, C.T. Yeh, C.H. Lin, V. Zima, Cryst. Growth Des. 11 (2011) 699. J.D. Lin, S.T. Wu, Z.H. Lia, S.W. Du, Dalton Trans. 39 (2010) 10719. Y.F. Han, Z.B. Zheng, C.A. Wang, J.F. Sun, X.Y. Li, J.P. Zhang, J. Xiao, G.F. He, L.Q. Li, J. Mol. Struct. 1079 (2015) 163.
Q. Nie et al. / Journal of Molecular Structure 1186 (2019) 434e439 [45] A. Ghaffari, M. Behzad, M. Pooyan, H.A. Rudbari, G. Bruno, J. Mol. Struct. 1063 (2014) 1. [46] Y.G. Huang, Y.F. Zhou, D.Q. Yuan, B.L. Wu, F.L. Jiang, M.C. Hong, J. Mol. Struct. 830 (2007) 85. [47] G.F. Xu, P. Gamez, J.K. Tang, R. Clerac, Y.N. Guo, Y. Guo, Inorg. Chem. 51 (2012) 5693.
439
mez, L. Vendier, M. Corbella, J.P. Costes, Inorg. Chem. 51 (2012) 6396. [48] V. Go [49] J. Lin, K. Diefenbach, M.A. Silver, N.S. Dalal, T.E. Albrecht-Schmitt, Cryst. Growth Des. 15 (2015) 4606. [50] Y.Y. Tang, M.Y. Cui, W.B. Guo, S.Y. Zhang, M. Yang, Z.Z. He, Cryst. Growth Des. 15 (2015) 2742.