Series of Lanthanide–Mercury Compounds with Three-Dimensional

Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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Series of Lanthanide−Mercury Compounds with Three-Dimensional Structures: Rational Preparation, Structures and Properties Wen-Tong Chen,* Zhuan-Xia Zhang, Hui Luo, Yan Sui, and Dong-Sheng Liu Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jinggangshan University, Ji’an, Jiangxi 343009, P. R. China

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S Supporting Information *

ABSTRACT: Three novel Ln−Hg complexes [Ln(H2O)2(μ-IA)3Hg3Br6]n (Ln = Pr (1), Nd (2), and Er (3); HIA is isonicotinic acid) are synthesized and characterized. They feature threedimensional (3-D) motifs. Solid-state UV/vis diffuse reflectance spectroscopy found that their band gaps are 4.91, 4.59, and 2.68 eV. It is found that lanthanide ions could adjust the band structures of semiconductors. Their photoluminescence comes from their characteristic emissions of 1D2 → 3H4 of Pr3+, 7F7/2 → 4S3/2 and 4F3/2 → 4I9/2 of Nd3+, and 4I15/2 → 4F7/2 and 4 I15/2 → 4S3/2 of Er3+. The CIE chromaticity coordinate is (x = 0.5726, y = 0.4206), (x = 0.7268, y = 0.2732), and (x = 0.2923, y = 0.4317). Their magnetization susceptibility totally obeys the Curie−Weiss equation with antiferromagnetic performances.

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types of organic coodinating species. In this research field, we have reported two Ln−IIB chloride compounds before, and they show fascinating performance.5 In this context, we report preparation, structures and performance of three novel Ln−Hg complexes [Ln(H2O)2(μ-IA)3Hg3Br6]n (Ln = Pr (1), Nd (2), and Er (3); HIA is isonicotinic acid). All of them obey Curie− Weiss equation and possess antiferromagnetic performances. In present work, it is found that the energy band gap values of complexes 1−3 obey the order of 1 > 2 > 3; it agrees with lanthanide contraction ranking. Based on this phenomenon, various lanthanide ions could result in various energy bandgaps; or in other words, lanthanide ions could regulate and control the band structures of semiconductors.

INTRODUCTION Lanthanide compounds are a very interesting research area and continuously attracted many researchers since many years ago, due to their fascinating luminescence, magnetization and other physicochemical performances.1 A lot of exploration has been plunged into investigating lanthanide compounds for revealing their valuable applications in a lot of fields, for instance, electroluminescence equipment, light emission apparatuses, photoluminescence detectors, magnetization instruments etc.2 Generally speaking, lanthanide compounds could likely emit excellent photoluminescence spectroscopy under the conditions of their f−f electrons could transfer among the orbitals, although not all lanthanide elements are luminescence. However, under most given circumstance lanthanide ions only bear very poor imbibing quotiety; this could hold back f−f electrons to transfer among the orbitals. In order to upgrade the imbibing quotiety, researchers introduce many types of organic species which possess conjugating conformation, for example, aromatic carboxylic acidic molecules or heterocyclic ligands as coodinating species into contrive fascinating lanthanide compounds. Researchers believe these coodinating species could imbibe and transmit light energy to central lanthanide atoms; it is “antenna effect”.3 As far as we know, compounds that comprise of IIB metals (zinc, cadmium, and mercury) are amusing because they own useful photoluminescence spectroscopy and semiconductive characteristics, interesting coordination modes and structural features which come from d10 comformation of IIB metals.4 For the sake of seeking after interesting MOFs (metal−organic frameworks) with fascinating structure characteristics and useful performance, for many years we have devoted ourselves to the investigating field of Ln−IIB MOFs by way of different © XXXX American Chemical Society

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RESULTS AND DISCUSSION Crystal Structures: [Ln(H2O)2(μ-IA)3Hg3Br6]n (Ln = Pr (1), Nd (2), and Er (3)). X-ray experimental results uncover the fact that complexes 1−3 were isomorphous. So, in this part only complex 2 is used as an example to describe their structures in detail. Complex 2 has three Hg2+, one Nd3+ ion, six Br− ions, two H2O and three IA− ligands. The Nd3+ ion is ligated by two OH2O atoms and six OIA− atoms to form a square antiprismatic comformation whose top and bottom planes are formed by O1W, O4, O2W, O3 (−x + 2, −y + 1, −z − 1) and O5 (−x + 5 /2, y + 1/2, −z − 1/2), O1(−x + 3/2, y + 1/2, −z − 1/2), O6 (x − 1/2, −y + 3/2, z − 1/2), and O2 (x + 1/2, −y + 3/2, z − 1/2) atoms (Figure 1). The Nd−OH2O is 2.600(10) Å and Received: June 26, 2018

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DOI: 10.1021/acs.inorgchem.8b01739 Inorg. Chem. XXXX, XXX, XXX−XXX

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with the literature.7 The N(2)−Hg(2)−N(3) bond angle is 158.9(2)°. The N−Hg−Br is 84.92(17)−157.5(2)° and the Br−Hg−Br bond angle is from 88.52(4) to 175.16(3)°. Bond valence studies reveal that Nd3+ ion has the +3 state [Nd(1) = 3.298], but all Hg atoms have the +2 state [Hg(1) = 2.233; Hg(2) = 2.132; Hg(3) = 2.196].8 Neighboring Hg(3) ions connect together by way of μ3-Br(4) ion to form an infinite mercury bromide chain extending along the b direction (Figure 2b). In complex 2 all IA− molecules are μ3-coordination. The lanthanide-isonicotinic acid chains and mercury bromide chains connect together by way of the IA− molecules to form a 3-D framework in which the one-dimensional (1-D) channels extending along the b direction (Figure 3).

Figure 1. ORTEP plot of 2. Symmetric codes: #1 −x + 5/2, y + 1/2, −z −1/2; #2 −x + 2, −y + 1, −z − 1; #3 x - 1/2, −y + 3/2, z − 1/2; #4 −x + 3/2, y + 1/2, −z - 1/2; #5 x + 1/2, −y + 3/2, z − 1/2.

2.511(11) Å, while Nd−Oisonicotinic acid is from 2.365(9) Å to 2.501(9) Å. The Nd−O bond length can be compared with the literature.6 The O−Nd−O is from 67.1(3)° to 144.2(3)°. Each Nd3+ ion connects two neighboring Nd3+ ions by way of bridging IA− ions in a vicissitudinary number of -four−two− four- to form a lanthanide−isonicotinic acid chain extending along the b direction (Figure 2a). Nd−Nd distances are 4.4859(7) and 5.2822(7) Å, which are very close distances and can generate magnetic interaction.

Figure 3. Packing view of 2 in a space-filling way.

Properties: Solid-State Diffuse Reflectance Spectroscopy. As far as we know, Hg is very useful because it has vital applications for photovoltaic materials, for instance, the wellknown MCT (Hg1−xCdxTe) that can be used in the military domain.9 It is known so far that many compounds possessing Hg could display semiconductor preformances.10 Therefore, it is supposed that complexes 1−3 could also show semiconductor preformances. Optical absorption spectroscopy found that the existence of energy band-gaps of 4.91, 4.59, and 2.68 eV for complexes 1, 2, and 3, respectively (Figure 4); this indicates that complexes 1−3 could be potentially wide band gap semiconductors. The energy band gap values of complexes 1−3 obey the order 1 > 2 > 3; it agrees with lanthanide contraction ranking. On the basis of this phenomenon, various lanthanide ions could result in various Figure 2. Chains in 2. (a) The lanthanide−isonicotinic acid chain and (b) the mercury bromide chain.

Hg1 is ligated by a terminal Br− ion, two μ2-Br− ions, and one NIA− atom to form a tetrahedral conformation. Hg2 ion is ligated by two μ2-Br− ions, a μ3-Br− ion, and two NIA− atoms to form a square pyramidal conformation. Hg3 is ligated by two terminal Br− ions and two μ3-Br− ions to form a tetrahedral conformation. The Hg−Brterminal is 2.4320(12), 2.4074(13), and 2.4269(14) Å, while the Hg−Brbridging value ranges from 2.8329(11) to 3.1241(13) Å, which is clearly larger than that of Hg−Brterminal. The Hg−Br bond length can be compared

Figure 4. Solid-state diffuse reflectance spectra of 1−3. B

DOI: 10.1021/acs.inorgchem.8b01739 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry energy band-gaps, or in other words, lanthanide ions could regulate and control the band structures of semiconductors. The reflectance spectra of 1−3 have several tiny peaks in the small energy gap region. These tiny peaks should be resulted from lanthanide ions. The lean of the optical absorption slopes for 1−3 is also in a sequence of 1 > 2 > 3. Compound 1 has a steep slope which suggests a direct transition, while coupounds 2 and 3 have a slow slope which suggests an indirect transition.11 Such a large optical absorption deviation in 1−3 should be a result of the increasing 4f electron numbers. Photoluminescence. As far as we know, materials which consist of Ln ions (for example, Pr3+, Nd3+, Sm3+, Eu3+, Tb3+, Dy3+, and Er3+) could exhibit fascinating photoluminescence performance because Ln ions feature abundant f-electrons.12 So, we reckon that complexes 1−3 could have photoluminescence performances. So, for the sake of validating this consideration, in this part, we will report the photoluminescence performances of complexes 1−3 that were measured using solid state compounds and the photoluminescence plots can be found in Figure 5. The effective energy absorption is almost resident at 350−450, 250−300, and 300−350 nm. Complex 1 has a broad photoluminescence emission band at 550−750 nm (the maximum value is equal to 610 nm), if photoexcited by 390 nm. It is the characteristic emission peaks of Pr3+ ions (1D2 → 3H4).13 Differently, complex 2 has two photoluminescence emission bands whose center is at 744 and 877 nm; this should result from the characteristic emission peaks of Nd3+ ions, i.e.. 7F7/2 → 4S3/2 and 4F3/2 → 4I9/2.14 Complex 3 also has two photoluminescence emission bands whose centers are at 489 and 541 nm; this should result from the characteristic emission peaks of Er3+ ions, i.e., 4I15/2 → 4F7/2 and 4I15/2 → 4S3/2, respectively.15 As a result, the photoluminescence spectra of 1−3 obviously result from the lanthanide 4f electrons intrashell transitions. CIE chromaticity coordinate for 1−3 is (x = 0.5726, y = 0.4206), (x = 0.7268, y = 0.2732) and with TSV being (X = 407235.576735998, Y = 299146.349163073, Z = 4868.62664102063), (X = 6297.70872159809, Y = 2367.02515483043, Z = 0.0621434871), and (X = 147122.323288739, Y = 217284.507611724, Z = 138972.198458505), and UCS1976 being (u′ = 0.3318, v′ = 0.5484), (u′ = 0.6026, v′ = 0.5096), and (u′ = 0.1539, v′ = 0.5115). The CIE plots are offered in Figure 6. Magnetic Properties. Variable-temperature magnetization measurements for 1−3 were studies using crystalline powders at 1000 Oe. The χM vs temperature and μeff vs temperature plots of 1 can be observed from Figure 7a. χM means magnetic susceptibility for each Pr3+ unit (Pr3+ ion: S = 4 at the 3H4 ground state). At 300 K, the μeff is equal to 18.15 μB, which is over five times larger than the expected one of 3.62 μB for each noninteracting free Pr3+ ion unit. This large difference validates that strong magnetic interaction could exist among Pr3+ ions; it is in good consistent with X-ray analysis results. If the temperature decreased, μeff also slowly decreases to 15.51 μB at 50 K, then abrupt decreases to 4.79 μB at 2 K. The χM vs temperature curve was fitted using the Curie−Weiss equation and the fitting C was 35.41 K and Weiss constant θ was negative and equal to −12.7 K; this suggests that complex 1 has antiferromagnetic performances. Lanthanide materials featuring antiferromagnetic performances are documented for many times.16 The χM vs temperature and μeff vs temperature plots for 2 is given in Figure 7b. χM means magnetic susceptibility for each Nd3+ ion unit (Nd3+ ion: S = 9/2 at

Figure 5. Photoluminescence spectroscopy of (a) 1 (excited by 390 nm), (b) 2 (excited by 288 nm), and (c) 3 (excited by 321 nm).

I9/2 ground state). At 300 K the μeff is equal to 23.07 μB, which is over six times larger than the expected one of 3.68 μB for each noninteracting free Nd3+ ion unit; this also suggests intensive magnetic coupling among Nd3+ ions. If the testing temperature is decreased, μeff continuously decreases to 13.24 μB (5 K) and increases to 13.50 μB (2 K). The χM vs temperature plot is also fitted using the Curie−Weiss equation, and the fitting C was 35.8 K and Weiss constant θ was also negative and equal to −18.8 K; this also suggests that complex 2 has antiferromagnetic performances. The χM vs temperature and μeff vs temperature of 3 is in Figure 7c. χM means magnetic susceptibility for each Er3+ unit (Er3+ ion: S = 3/2 at 4S3/2 ground state). μeff is 29.03 μB (300 K), three times bigger than 4

C

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Figure 7. Temperature correlation of χM and μeff for (a) 1, (b) 2, and (c) 3. Red lines are the theoretical lines based on the Curie−Weiss equation.

temperature decreased, μeff continuously decreases to 27.27 μB at 25 K, then increases to 27.59 μB at 14 K, followed by a decrease to 27.22 μB at 6K and, finally, abruptly increases to 29.15 μB at 2 K. This could be probably resulted from the zerofield splitting phenomenon.17 The χM vs temperature plot is also fitted using Curie−Weiss equation and the fitting C is 95.6 K and Weiss constant θ is negative and equal to −0.82 K; this also suggests antiferromagnetic performances. The nature of these antiferromagnetic performances of 1−3 is still needed to be clarified, but it could be possibly originating from the progressively depopulating Stark compositions of Ln ion.18 Figure 8 presents the field correlation of magnetization for 1−3 at 2 K. The sigmoidal shape of 1, 2, and 3 is more and

Figure 6. CIE plots of (a) 1, (b) 2, and (c) 3.

expected of 9.6 μB for each noninteracting free Er3+ ion unit; this also indicates intensive coupling among Er3+ ions. If the D

DOI: 10.1021/acs.inorgchem.8b01739 Inorg. Chem. XXXX, XXX, XXX−XXX

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Oe and the value is equal to 2.17 Nβ. The M vs H plot uncovered that complex 2 has also a tiny coercive field (34 Oe) and a tiny remnant magnetization (∼2.6 × 10−3 Nβ). Once the magnetic field was increased, the magnetization of complex 3 rapidly ascends to 2.31 Nβ at 15000 Oe, and then tardily ascends to 2.77 Nβ at 80000 Oe (Figure 8c). The M vs H plot of complex 3 revealed that the magnetization is close to saturate at 80000 Oe and the value is equal to ∼2.77 Nβ. The M vs H plot uncovered that complex 3 has also a tiny coercive field (∼36 Oe) and a tiny remnant magnetization (1.5 × 10−2 Nβ). Obviously, both coercive field and remnant magnetization of complexes 1−3 are according to the sequence of 1 < 2 < 3, which is also well consistent with the lanthanide contraction sequence of Pr, Nd and Er.

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CONCLUSION A series of novel Ln−Hg complexes were reported. They feature 3-D structural conformation. Solid-state UV/vis diffuse reflectance spectroscopy revealed that they possess energy band-gaps of 4.91, 4.59, and 2.68 eV. It is found that the energy band gap values of complexes 1−3 obey the order 1 > 2 > 3; this agrees with the lanthanide contraction ranking of Pr, Nd, and Er. On the basis of this phenomenon, various lanthanide ions could result in various energy band-gaps; or in other words, lanthanide ions could regulate and control the band structures of semiconductors. Their photoluminescence emissions should be resulted from their characteristic 4f emission peaks of Pr3+ ions (1D2 → 3H4), Nd3+ ions (7F7/2 → 4 S3/2 and 4F3/2 → 4I9/2), and Er3+ ions (4I15/2 → 4F7/2 and 4I15/2 → 4S3/2). Their variable-temperature magnetization plots totally obey the Curie−Weiss equation and they feature antiferromagnetic preformance. Future exploration in our group will keep focusing on Ln−IIB mixed metal materials, to probe into the relationship among the molecular structures, synthesis, and behaviors.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b01739. Experimental information, crystal data, and bond lengths and angles (PDF) Accession Codes Figure 8. Magnetization−field of (a) 1, (b) 2 and (c) 3.

CCDC 1818356−1818358 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

more clear. At 80000 Oe the M value is also increased according to the sequence of complexes 1, 2, and 3. It agrees well with lanthanide contraction ranking. The explanation for this phenomenon could be possibly the increase of the lanthanide 4f electron numbers. The magnetization of complex 1 ascends tardily with the ascending magnetic field (Figure 8a). The M vs H plot of complex 1 uncovered that the magnetization is not saturated yet even at 80000 Oe and the value is equal to 0.89 Nβ. The M vs H plot uncovered that complex 1 features a tiny coercive field (∼30 Oe) and a tiny remnant magnetization (∼3.6 × 10−4 Nβ). Once the magnetic field was increased, the magnetization of complex 2 abruptly ascends to 1.88 Nβ at 30000 Oe and then tardily ascends to 2.17 Nβ at 80000 Oe (Figure 8b). The M vs H plot of complex 2 revealed that the magnetization is close to saturate at 80000

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AUTHOR INFORMATION

Corresponding Author

*(W.-T.C.) Fax: (+86)-796-8100490. E-mail: wtchen_2000@ aliyun.com. ORCID

Wen-Tong Chen: 0000-0002-3486-1875 Yan Sui: 0000-0002-3936-4026 Notes

The authors declare no competing financial interest. E

DOI: 10.1021/acs.inorgchem.8b01739 Inorg. Chem. XXXX, XXX, XXX−XXX

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ACKNOWLEDGMENTS This workis supported by Grant No. GJJ170637 from the Jiangxi Province Education Department and Technology and Grant No. of 20180008 from the State Laboratory of Structural Chemistry, FJIRSM, CAS.

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DOI: 10.1021/acs.inorgchem.8b01739 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b01739 Inorg. Chem. XXXX, XXX, XXX−XXX