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Communication

Hetero-Trinuclear CoII2-DyIII Complex with a Octadentate Bis(Salamo)-Like Ligand: Synthesis, Crystal Structure and Luminescence Properties

School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China
*
Author to whom correspondence should be addressed.
Crystals 2018, 8(4), 174; https://doi.org/10.3390/cryst8040174
Submission received: 28 March 2018 / Revised: 15 April 2018 / Accepted: 16 April 2018 / Published: 18 April 2018
(This article belongs to the Section Crystal Engineering)

Abstract

:
A hetero-trinuclear CoII2-DyIII complex, [Co2L(DMF)2Dy(NO3)3]·C2H5O2 was synthesized via the reaction of a multi-naphthol-based bis(Salamo)-like tetraoxime H4L with Co(OAc)2·4H2O and Dy(NO3)3·6H2O, and fully characterized via elemental analyses, X-ray crystallography, FT-IR and UV-Vis spectra. In addition, luminescence properties of H4L and its CoII2-DyIII complex have also been investigated.

Graphical Abstract

1. Introduction

In the past decades, many scientists were working on the study of Salen [1,2,3] and its analogues [4,5,6,7,8,9] mainly because their metal complexes can be widely used in obtaining optical [10,11,12,13] and magnetic [14] materials, biological fields [15,16,17,18,19,20,21], electrochemistry [15,16,17,18,19,20,21,22,23], ion recognition [24,25,26,27,28,29,30,31,32], supra-molecular buildings [33,34], catalysis activities [35,36,37,38], and so on. In the present study, some appropriate Salen-like compounds (Salamo and its analogues) were selected as a hot topic and there are many reports about the metal complexes including two or more molecules of Salen-like ligands [39,40,41,42]. Chemical modifications of substituent or functional groups in the Salen N2O2 ligands are effective in exchanging the structures or the main functions of the complexes, such as Salamo N2O2 ligand (1,2-Bis(salicylideneaminooxy)ethane), a Salen’s analogue, (R–CH=N–O–(CH)n–O–N=CH–R) one of the most versatile ligands [37,43]. Although some Salamo-like complexes have been described, there are poorly reported polynuclear hetero-bimetallic 3d–4f complexes with interesting structures and optical properties [44,45,46,47,48]. Moreover, a key feature of such structures is that trivalent lanthanide ions have higher coordination numbers, larger radius, more flexible coordination geometries and unusual 4f electron construction with larger spin moments and stronger spin-orbit coupling [49], therefore, the lanthanide metal complexes have shown interesting magnetic [50] and distinct luminescent properties [51,52,53,54]. In addition, 3d–4f complexes can be widely used in catalysis filed [55,56,57,58,59,60,61].
In order to study further the hetero-bimetallic 3d–4f Salamo-like complexes and their optical properties, we have newly designed a novel hetero-trinuclear CoII2-DyIII complex by the complexation of a multi-naphthol-based symmetric bis(Salamo)-like tetraoxime H4L with Co(OAc)2·4H2O and Dy(NO3)3·6H2O.

2. Experimental Section

2.1. Materials and Physical Measurements

2-Hydroxy-3-methoxybenzaldehyde, 2-hydroxy-1-naphthaldehyde, methyl trioctyl ammonium chloride, borontribromide and pyridiniumchlorochromate were obtained from Alfa Aesar (New York, NY, USA). The other reagents and solvents were bought from Shanghai Darui Chemical Fine Chemicals Company (Tianjin, China). Solvents and all other chemicals were of analytical grade and used without further purification. Elemental analyses (C, H and N) were carried out with Elemantar GmbH VarioEL V3.00 automatic elemental analysis equipment (Berlin, Germany). Elemental analyses for CoII and DyIII atoms were measured using an IRIS ER/S·WP-1 ICP atomic emission spectrometer (Berlin, Germany). Melting points were measured using an X4 microscopic melting point apparatus made by Beijing Taike Instrument Limited Company (Beijing, China) and were not corrected. FT-IR spectra were recorded on a VERTEX70 FT-IR spectrophotometer (Bruker, Billerica, MA, USA), with samples prepared as KBr (400–4000 cm−1). UV-Vis absorption spectra in the 200–600 nm range were measured on a Hitachi U-3900H spectrophotometer (Shimadzu, Japan) in mixed solvent (chloroform/methanol = 3:2, v/v). Fluorescent spectra were taken on F-7000 FL spectrophotometer (Shimadzu, Japan). 1H NMR spectra were measured using a German Bruker AVANCE DRX-400 spectrometer (Bruker, AVANCE, Billerica, MA, USA). X-ray single crystal structure was determined via a Bruker Smart Apex CCD diffractometer (Bruker, AVANCE, Billerica, MA, USA).

2.2. Synthesis and Characterization of the Ligand H4L

H4L was synthesized according to the early reported method, the 1H NMR (Figure 1), IR and UV-Vis spectra of H4L are in consistent with the data [62].
The step included in the synthetic route to the CoII2-DyIII complex is shown in Scheme 1.

2.3. Synthesis of the CoII2-DyIII Complex

A solution of Co(OAc)2·4H2O (14.94 mg, 0.06 mmol) in methanol (2 mL) and Dy(NO3)3·6H2O (9.13 mg, 0.02 mmol) in methanol (1 mL) were added to a solution of H4L (13.44 mg, 0.02 mmol) in acetone/DMF (1:1, 1 mL) with constant stirring. After about 30 min later, the color of the mixture turned to brown immediately, the brown mixture obtained was filtered and the filtrate was kept undisturbed at diethyl ether. One week later, clear dark brown block-like crystals suitable for X-ray diffraction were formed and carefully collected by filtration, washed with 2:1 (v/v) acetone:hexane, and dried at room temperature. Yield: 46%. IR (KBr; cm−1): 1594 [v(C=N), s], 1249 [v(Ar–O), s]. Anal. Calcd. for C52H62Co2DyN9O21 (%): C, 43.69; H, 4.37; N, 8.82; Co., 8.25; Dy, 11.37. Found: C, 43.91; H, 4.56; N, 8.56; Co., 8.03; Dy, 11.21.

2.4. X-ray Structure Determination of the CoII2-DyIII Complex

The single crystal of the CoII2-DyIII complex with approximate dimensions of 0.26 × 0.24 × 0.23 mm, was placed on Bruker Smart 1000 CCD area detector. The crystal diffraction data were collected using a graphite monochromated Mo Kα radiation (λ = 0.071073 nm) at 293(2) K. The structure was solved the using the program SHELXS-2015 and Fourier difference techniques, and refined by full-matrix least-squares method on F2 using SHELXL-2015 [63]. Hydrogen atoms were fixed at calculated positions, and their positions were refined by a riding model. Details of the data collection and refinements are presented in Table 1.

3. Results and Discussion

3.1. IR Spectra of H4L and Its Corresponding CoII2-DyIII Complex

The FT-IR spectra of H4L and its corresponding CoII2-DyIII complex exhibited various bands in the range of 400–4000 cm−1. As depicted in Figure 2, H4L showed a typical C=N stretching band at ca. 1613 cm−1 [64,65], while the C=N stretching band of the CoII2-DyIII complex was observed at ca. 1594 cm−1. The shift to lower frequency by ca. 19 cm−1 upon complexation shows a decrease in the C=N bond order due to the coordinative bonds of the metal atom with the oxime nitrogen lone pair [66]. The Ar–O typical stretching band of H4L appeared as a strong band at ca. 1258 cm−1, but was observed at ca. 1249 cm−1 for the CoII2-DyIII complex and shift to lower frequency by ca. 9 cm−1 in the CoII2-DyIII complex, exhibiting that the Co-OAr and Dy-OAr bonds were formed between phenolic oxygen atoms and the metal atoms [67,68,69]. Besides, the coordinated nitrate groups appeared at ca. 1300 cm−1 for the CoII2-DyIII complex [23]. Furthermore, the O–H stretching bands appeared at ca. 3419 cm−1 in H4L [70], and disappeared in the CoII2-DyIII complex.

3.2. UV-Vis Absorption Spectra of H4L and Its Corresponding CoII2-DyIII Complex

UV-Vis spectra of H4L and its corresponding CoII2-DyIII complex in mixed solutions (chloroform/methanol = 3:2, v/v) at 298 K are shown in Figure 3. The spectrum of H4L was almost consistent with the reported earlier [62]. In the UV–Vis titration experiments of CoII2-DyIII complex, the color of the solution of CoII complex in mixed solutions (chloroform/methanol = 3:2, v/v) changed inconspicuously when the solution of DyIII ion was added. However, the CoII2-DyIII complex displayed three absorption bands at ca. 317, 374, and 419 nm, which shown red-shifted and indicate the coordination of H4L with metal ions [70,71,72,73,74]. In addition, the molar absorption coefficient at 374 and 322 nm for the CoII2-DyIII complex in mixed solutions (chloroform/methanol = 3:2, v/v) are 29,200 and 18,900 M−1·cm−1, respectively. As in the case for the CoII2-DyIII complex, although H4L has two Salamo chelate units, the titration curves clearly indicated that the stoichiometry between DyIII ion and [LCo3]2+ was 1:1, and the isosbestic points (319, 351 and 401 nm) were observed.

3.3. Description of Crystal Structure of the CoII2-DyIII Complex

The crystal structure of the CoII2-DyIII complex and the coordination environment of CoII and DyIII atoms are shown in Figure 4. Selected bond lengths and angles are summed in Table 2.
X-ray structure analysis showed the CoII2-DyIII complex crystallizes in the monoclinic system, space group P121/m1 with cell dimensions a = 9.2838(4), b = 24.9653(11), c = 12.7982(6), and Z = 2. It is composed of two CoII atoms, one DyIII atom, one deprotonated (L)4- unit, three coordinated nitrate groups, and two coordinated N,N-dimethylformamide molecules resulting in a hetero-trinuclear CoII2-DyIII complex. In the CoII2-DyIII complex, two terminal CoII atoms are both six-coordinated with geometries of slightly distorted octahedron. The inner N2O2 coordination spheres of Salamo moieties were occupied by two terminal Co1 and Co1# atoms, meanwhile, two bidentate nitrate groups coordinated two terminal CoII atoms. DyIII is sited in the O4 cavity that includes four phenoxy oxygen atoms (O1, O4, and O1#, O4#). Besides, the two coordinated DMF molecules provide two oxygen atoms (O11 and O12) and the bidentate nitrate groups provide remaining two oxygen atoms (O8 and O6), so DyIII is eight–coordinated and possesses a distorted square antiprism geometry. Compared with our previously reported CoII complex [62], CoII atoms are in N2O2 coordination environments, and particularly the CoII atoms are chelated further with one bidentate nitrate group. The distance between the two terminal metal atoms Co1-Co1# is 6.322(3), in the previously reported CoII complex the distance of Co1-Co3 is 6.304(3). The distance of Co1-Co1# is longer than previously reported, because the larger radius DyIII atom replaced the central CoII atom. The angles of O2-N1-C11, O1-C1-C2 and C10-C11-N1 are 113.7(3), 116.8(4) and 123.3(4), respectively, indicating that the ligand H4L is more flexible.

3.4. Supramolecular Interactions of the CoII2-DyIII Complex

Notably, there are various intra- and inter-molecular hydrogen bond interactions in the crystal structure of the CoII2-DyIII complex. The hydrogen bond parameters are summed in Table 3. As shown in Figure 5.
There are three pairs of intra-molecular hydrogen bond interactions (C13–H13B···O6, C20–H20···O12 and C22–H22B···O11) [75,76]. Besides, the structure of the CoII2-DyIII complex is stabilized by inter-molecular O–H···O, C–H···O and C–H···π hydrogen bond interactions. As a result, the CoII2-DyIII complex possesses a self-assembling infinite 2D and 3D supra-molecular structure [77] via the inter-molecular hydrogen bonds, respectively (Figure 6). The 3D supra-molecular structure of the CoII2-DyIII complex includes two parts. The former is linked via inter-molecular O–H···O and C–H···O hydrogen bond interactions. The latter is composed of the C–H···π interactions. The inter-molecular hydrogen bonding of the CoII2-DyIII complex makes its structure variable and stable. There is no π···π interactions in the CoII2-DyIII complex because the distance between ring centroids was 5.953(2) which beyond the specified range.

3.5. Fluorescence Properties of the CoII2-DyIII Complex

The emission spectra of H4L and its CoII2-DyIII complex in dilute DMF solution at room temperature are depicted in Figure 7. H4L showed an intense photoluminescence with maximum emission at ca. 431 nm when excited at ca. 372 nm, which can be attributed to intra-ligand π–π* transitions. Meanwhile, compared with H4L, the CoII2-DyIII complex showed slightly weaker fluorescence intensity with maximum emissions at ca. 421 nm upon excitation at ca. 372 nm, which are attributed to the intra-ligand π–π* transition and exhibiting that the fluorescent behaviour has been affected by the CoII atoms [78]. The bathochromic indicates the hetero-trinuclear structure led to a larger conjugate system [72].

4. Conclusions

We have newly designed a novel hetero-trinuclear CoII2-DyIII complex with a multi-naphthol-based bis(Salamo)-like tetraoxime H4L. The CoII2-DyIII complex has been characterized via X-ray diffraction and physicochemical methods. In the CoII2-DyIII complex, two terminal CoII atoms, sited in the N2O2 cavities of the Salamo units, bear distorted octahedral geometries, and the central O4 coordination environment was occupied by the DyIII atom bearing a distorted square antiprism. Significantly, the CoII2-DyIII complex possesses a self-assembling infinite 2D and 3D supra-molecular structure through the inter-molecular hydrogen bondings which make its structure variable and stable. Compared with H4L, the CoII2-DyIII complex exhibited slightly lower fluorescence intensity, and shifted to higher wavelength, indicating the hetero-trinuclear structure led to a larger conjugate system.

Supplementary Materials

The crystallographic data is available online at https://www.mdpi.com/2073-4352/8/4/174/s1.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21761018) and the Program for Excellent Team of Scientific Research in Lanzhou Jiaotong University (201706), both of which are gratefully acknowledged.

Author Contributions

Yu-Hua Yang and Jing Hao performed most of the experiments. Xiao-Yan Li and Yang Zhang contributed to the writing of the manuscript. Wen-Kui Dong designed the project. All authors reviewed the manuscript.

Conflicts of Interest

The authors declare no competing financial interests.

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Figure 1. 1H NMR spectrum of the ligand H4L (CDCl3, 400 MHz).
Figure 1. 1H NMR spectrum of the ligand H4L (CDCl3, 400 MHz).
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Scheme 1. Synthetic route to the CoII2-DyIII complex.
Scheme 1. Synthetic route to the CoII2-DyIII complex.
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Figure 2. IR spectra of H4L and its corresponding CoII2-DyIII complex.
Figure 2. IR spectra of H4L and its corresponding CoII2-DyIII complex.
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Figure 3. (a) UV-Vis absorption spectra of H4L (c = 1 × 10−5 M). (b) Absorption spectra of the CoII2-DyIII complex in the presence of different concentrations of DyIII ion in mixed solutions (chloroform/methanol = 3:2, v/v) at 298 K.
Figure 3. (a) UV-Vis absorption spectra of H4L (c = 1 × 10−5 M). (b) Absorption spectra of the CoII2-DyIII complex in the presence of different concentrations of DyIII ion in mixed solutions (chloroform/methanol = 3:2, v/v) at 298 K.
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Figure 4. (a) Molecular structure of the CoII2-DyIII complex. (b) The coordination polyhedrons for CoII and DyIII atoms.
Figure 4. (a) Molecular structure of the CoII2-DyIII complex. (b) The coordination polyhedrons for CoII and DyIII atoms.
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Figure 5. Intramolecular hydrogen bonding interactions of the CoII2-DyIII complex.
Figure 5. Intramolecular hydrogen bonding interactions of the CoII2-DyIII complex.
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Figure 6. Part of the infinite 2D supra-molecular structure along a axis (a); c axis (b); C–H···π (c) and 3D (d) supra-molecular structure of the CoII2-DyIII complex with intermolecular hydrogen bondings (hydrogen atoms, except those forming hydrogen bonds, are omitted for clarity).
Figure 6. Part of the infinite 2D supra-molecular structure along a axis (a); c axis (b); C–H···π (c) and 3D (d) supra-molecular structure of the CoII2-DyIII complex with intermolecular hydrogen bondings (hydrogen atoms, except those forming hydrogen bonds, are omitted for clarity).
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Figure 7. Fluorescence spectra of H4L and its CoII2-DyIII complex (c = 1 × 10−5 M) upon excitation at ca. 372 nm in mixed solutions (chloroform/methanol = 3:2, v/v) at 298 K.
Figure 7. Fluorescence spectra of H4L and its CoII2-DyIII complex (c = 1 × 10−5 M) upon excitation at ca. 372 nm in mixed solutions (chloroform/methanol = 3:2, v/v) at 298 K.
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Table 1. Crystal data and structure refinements for the CoII2-DyIII complex.
Table 1. Crystal data and structure refinements for the CoII2-DyIII complex.
[Co2L(DMF)2Dy(NO3)3]·C2H5O2
FormulaC52H62Co2DyN9O21
Formula weight1429.46
Temperature (K)293(2)
Wavelength (Å)0.71073
Crystal systemmonoclinic
Space groupP121/m1
a (Å)9.2838(4)
b (Å)24.9653(11)
c (Å)12.7982(6)
β (°)97.059(4)°
V(Å3)2943.8(2)
Z2
Dcalc (g·cm−3)1.613
µ (mm−1)1.897
F (000)1450
Crystal size (mm)0.26 × 0.24 × 0.23
θ Range (°)3.310–26.017
−11 ≤ h ≤ 10
Index ranges−30 ≤ k ≤ 25
−15 ≤ l ≤ 11
Reflections collected11,948
Independent reflections5933
Rint0.0456
Completeness to θ99.7% (θ = 26.32)
Data/restraints/parameters5933/3/422
GOF1.028
Final R1, wR2 indices [I > 2σ(I)]0.0426/0.0758
Final R1, wR2 indices (all data)0.0590/0.0854
Largest differences peak and hole (e Å−3)0.840/−1.044
Supplementary crystallographic data for this paper have been deposited at Cambridge Crystallographic Data Centre (1817410) and can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html.
Table 2. Selected bond lengths (Å) and angles (°) for the CoII2-DyIII complex.
Table 2. Selected bond lengths (Å) and angles (°) for the CoII2-DyIII complex.
BondLengthsBondLengthsBondLengths
Dy1–O1#12.339(3)Dy1–O92.480(4)Co1–O12.104(3)
Dy1–O12.339(3)Dy1–O112.316(3)Co1–O41.983(3)
Dy1–O4#12.383(2)Dy1–O122.275(5)Co1–O52.210(3)
Dy1–O42.383(2)Dy1–O12#12.275(5)Co1–O62.159(3)
Dy1–O82.400(4)Dy1–N42.861(5)Co1–N12.034(3)
BondAnglesBondAnglesBondAngles
O1#1–Dy1–O1158.66(13)O9–Dy1–N426.13(13)O12–Dy1–O1176.66(17)
O1#1–Dy1–O4132.84(9)O11–Dy1–O1#180.97(6)O12#1–Dy1–O1176.66(17)
O1–Dy1–O468.05(9)O11–Dy1–O180.97(6)O12#1–Dy1–O1218.2(5)
O1–Dy1–O4#1132.84(9)O11–Dy1–O4142.30(8)O12–Dy1–N4170.7(2)
O1#1–Dy1–O4#168.05(9)O11–Dy1–O4#1142.30(8)O12#1–Dy1–N4170.7(2)
O1–Dy1–O891.00(7)O11–Dy1–O8127.46(15)O1–Co1–O5100.03(12)
O1#1–Dy1–O891.00(7)O11–Dy1–O975.60(14)O1–Co1–O691.67(12)
O1#1–Dy1–O982.29(7)O11–Dy1–N4101.74(15)O4–Co1–O180.49(11)
O1–Dy1–O982.29(7)O12–Dy1–O1102.3(2)O4–Co1–O591.68(12)
O1–Dy1–N486.31(7)O12#1–Dy1–O1#1102.3(2)O4–Co1–O6147.62(12)
O1#1–Dy1–N486.31(7)O12–Dy1–O1#184.4(2)O4–Co1–N1111.71(12)
O4#1–Dy1–O464.84(12)O12#1–Dy1–O184.4(2)O4–Co1–N287.13(12)
O4#1–Dy1–O875.65(11)O12–Dy1–O4#179.37(18)O6–Co1–O558.58(12)
O4–Dy1–O875.65(11)O12#1–Dy1–O479.37(18)N1–Co1–O182.90(12)
O4–Dy1–O9118.79(10)O12#1–Dy1–O4#189.13(18)N1–Co1–O5156.54(14)
O4#1–Dy1–O9118.79(10)O12–Dy1–O489.13(18)N1–Co1–O698.23(13)
O4#1–Dy1–N497.30(12)O12#1–Dy1–O8154.48(18)N1–Co1–N294.30(13)
O4–Dy1–N497.30(12)O12–Dy1–O8154.48(18)N2–Co1–O1165.20(12)
O8–Dy1–O951.86(14)O12#1–Dy1–O9150.76(17)N2–Co1–O588.34(13)
O8–Dy1–N425.73(14)O12–Dy1–O9150.76(17)N2–Co1–O6103.12(13)
Symmetry transformations used to generate equivalent atoms: #1 x, 1/2-y, z.
Table 3. Hydrogen bonding interactions (Å, °) for the CoII2-DyIII complex a.
Table 3. Hydrogen bonding interactions (Å, °) for the CoII2-DyIII complex a.
D–H···AH···AD···AD–H···ASymmetry Codes
C13–H13B··· O62.583.497(6)158
C20–H20··· O122.533.041(8)115
O8–H8 ···O72.573.378(6)1451-x, 1-y, -z
O12–H12A ···O72.513.476(6)1741-x, 1-y, -z
C20–H20··· O102.543.403(7)154-1+x, y, z
C21–H21A··· O102.463.358(9)155-1+x, y, z
C21–H21C··· O132.463.421(6)176x, 1/2-y, z
C13–H13A··· Cg12.79 1401-x, 1-y, -z
C27–H27A··· Cg22.70 167x, y, z
C24–H24C··· Cg32.72 122-1+x, 1/2-y, z
C22–H22B··· Cg42.97 107x, 1/2-y, 1+z
a Cg1, Cg2, Cg3 and Cg4 for the CoII2-DyIII complex are the centroids of C1–C4, C9, C10; C4–C9; C15, C16, C16#, 15#, C17#, C17and C17–C19, 19#–C17# atoms, respectively.

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MDPI and ACS Style

Yang, Y.-H.; Hao, J.; Li, X.-Y.; Zhang, Y.; Dong, W.-K. Hetero-Trinuclear CoII2-DyIII Complex with a Octadentate Bis(Salamo)-Like Ligand: Synthesis, Crystal Structure and Luminescence Properties. Crystals 2018, 8, 174. https://doi.org/10.3390/cryst8040174

AMA Style

Yang Y-H, Hao J, Li X-Y, Zhang Y, Dong W-K. Hetero-Trinuclear CoII2-DyIII Complex with a Octadentate Bis(Salamo)-Like Ligand: Synthesis, Crystal Structure and Luminescence Properties. Crystals. 2018; 8(4):174. https://doi.org/10.3390/cryst8040174

Chicago/Turabian Style

Yang, Yu-Hua, Jing Hao, Xiao-Yan Li, Yang Zhang, and Wen-Kui Dong. 2018. "Hetero-Trinuclear CoII2-DyIII Complex with a Octadentate Bis(Salamo)-Like Ligand: Synthesis, Crystal Structure and Luminescence Properties" Crystals 8, no. 4: 174. https://doi.org/10.3390/cryst8040174

APA Style

Yang, Y. -H., Hao, J., Li, X. -Y., Zhang, Y., & Dong, W. -K. (2018). Hetero-Trinuclear CoII2-DyIII Complex with a Octadentate Bis(Salamo)-Like Ligand: Synthesis, Crystal Structure and Luminescence Properties. Crystals, 8(4), 174. https://doi.org/10.3390/cryst8040174

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