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Feb 13, 2018 - Stepwise ortho Chlorination of Carboxyl Groups for Promoting. Structure Variance of Heterometallic Uranyl−Silver Coordination. Polyme...
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Article Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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Stepwise ortho Chlorination of Carboxyl Groups for Promoting Structure Variance of Heterometallic Uranyl−Silver Coordination Polymers of Isonicotinate Lei Mei,† Kong-qiu Hu,† Zhi-hui Zhang,†,§ Shu-wen An,† Zhi-fang Chai,† and Wei-qun Shi*,† †

Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou 213164, China

§

S Supporting Information *

ABSTRACT: We report the syntheses and characterization of four new heterometallic uranyl−silver compounds from isonicotinic acid derivatives with a stepwise ortho chlorination of carboxyl group, that is, isonicotinic acid (H-PCA), 3chloroisonicotinic acid (H-3-MCPCA), and 3,5-dichloroisonicotinic acid (H-3,5DCPCA). Compound 1, (UO2)Ag4(3,5-DCPCA)6(3,5-DCPy)2, from H-3,5DCPCA displays a heterometallic three-dimensional (3D) framework through the connection of 3,5-DCPCA and in situ-formed 3,5-dichloropyridine (3,5-DCPy) with the aid of multiple argentophilic interactions. Compounds 2 ((UO2)Ag(3MCPCA)3) and 3 ((UO2)Ag2(3-MCPCA)4), which differ from each other in coordination modes of uranyl center, are both heterometallic 3D reticular frameworks from 3-MCPCA based on highly coordinated silver nodes. All these heterometallic uranyl−silver compounds are different from the hydrothermal products from chlorine-free H-PCA ligand in the presence of uranyl and silver ions, U−Ag-PCA ((UO2Ag(OH)(PCA)2)) and 4 ((UO2)Ag2(OH)(H2O)2(PCA)4) due to highly coordinated silver ions found in 1−3, among which carboxyl groups of isonicotinate expected to coordinate with uranyl are the biggest contributors. Detailed structural analysis reveals that the inclination of the carboxyl group of isonicotinate driven by large steric hindrance from bulky ortho chlorine atoms at its ortho positions enables it to participate in the coordination sphere of silver ion and promote the formation and structure variance of 3D heterometallic uranyl−silver frameworks.

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INTRODUCTION As one of the most important actinides in nuclear fuel cycles, uranium has drawn much attention from chemists, and significant efforts have been devoted to the exploration of the sophisticated knowledge of uranium−ligand interactions in solution and solid.1−3 Uranium−organic hybrid materials,4−7 largely based on the frequently encountered linear uranyl (UO22+) cation, provide much information on uranyl speciation under different conditions and uranyl coordination with variable organic ligands by abundant molecule structures and topologies, and meanwhile present intriguing physicochemical properties, showing potential application in many fields such as photochemical catalysis,7−10 pollutant removal,11−13 or radiation detection.14 When a second metal node or more modes are introduced into the uranyl−organic system through the utilization of multifunctional ligand that coordinates with uranyl and other metal nodes by different types of coordination sites, the library of uranyl−organic compounds will be greatly expanded by the resulting heterometallic uranyl−organic compounds, and new assembly modes and properties can be brought in subsequently.15−28 For example, isonicotinic or nicotinic acid derivatives can serve as good examples of multifunctional ligand, where uranyl ions usually show high binding affinities toward O-donor containing carboxyl groups, © XXXX American Chemical Society

while transition metal ions prefer to bind N-donor groups, that is, pyridyl groups, and several heterometallic uranyl−isonicotinate or uranyl−nicotinate compounds have been reported with both uranyl and other metal ions involved.18,22,29 The utilization of halogenated ligands in the syntheses of actinide−organic hybrid materials, which was first reported by Cahill et al.,30−36 is a special strategy to construct new actinide− organic hybrid materials through successful incorporation of halogen bonds as additional weak bond forces for intermolecular interactions and crystal packing. Our group is also interested in the construction of homometallic and heterometallic uranyl− organic compounds through a halogenation strategy employing halogenated isonicotinic acids as multifunctional ligands.18,37 For instance, a heterometallic uranyl−silver compound, namely, U− Ag-2,6-DCPCA,18 with threefold interpenetrating networks has been successfully prepared from 2,6-dichloroisonicotinic acid (H-2,6-DCPCA) and uranyl in the presence of silver ions (Scheme 1a). Interestingly, our previous results reveal that halogen atoms brought into the actinide−organic compounds not only have an effect on their intermolecular interactions but also exert a strong impact on the coordination behaviors of Received: February 13, 2018

A

DOI: 10.1021/acs.inorgchem.8b00402 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Scheme 1a

ortho positions eables it to participate in the coordination sphere of highly coordinated silver ion. A comprehensive comparison of these compounds with other previously reported homometallic or heterometallic analogues concerned with synthesis conditions and structure factors (halogen substitution) was also conducted to further unveil the contribution of varying halogenation patterns and second metal ion (i.e., silver ion) for structual difference between them. Moreover, IR spectra and luminescence properties of typical compounds were also studied.

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EXPERIMENTAL SECTION

Materials and Methods. Caution! Because of the radioactive and chemically toxic features of uranyl nitrate hexahydrate source, UO2(NO3)2· 6H2O, suitable measures for precautions and protection should be taken all over the experimental process. All the chemical reagents are commercially available and used without any further purification. Powder X-ray diffraction measurements (PXRD) were recorded on a Bruker D8 Advance diffractometer with Cu Kα radiation (λ = 1.5406 Å) in the range of 5−50° with a step size of 0.02°. The fluorescence spectra were measured on a Hitachi F-4600 fluorescence spectrophotometer equipped with a xenon lamp and solid sample holder, and a wavelength of 420 nm suitable for uranyl excitation was selected. The photomultiplier tube voltage was 700 V, the excitation and the emission slit width were 5.0 and 5.0 nm, respectively, and the scan speed was set as 60 nm per minute. The Fourier transform infrared (IR) spectra were recorded from KBr pellets in the range of 4000−400 cm−1 on a Bruker Tensor 27 spectrometer. Synthesis. All the uranyl compounds 1−4 were synthesized under hydrothermal conditions using a previously reported method with minor modification.18 (UO2)Ag4(3,5-DCPCA)6(3,5-DCPy)2 (1). UO2(NO3)2·6H2O aqueous solution (0.5 M; 200 μL, 0.1 mmol) and 1 M AgNO3 aqueous solution (100 μL, 0.1 mmol) were added to a suspension of H-3,5-DCPCA (0.056 g, 0.2 mmol) in water (1 mL) in a stainless steel bomb. After it was treated with ammonium hydroxide (10 μL), the mixture was sealed, kept at 150 °C for 48 h, and cooled to room temperature. The resulting yellow block crystals of 1 were filtered off, rinsed with water, and subjected to air-drying at room temperature. Yield: 12.2 mg, 5.7% based on uranium. (UO 2 )Ag(3-MCPCA) 3 (2) and (UO 2 )Ag 2 (3-MCPCA) 4 (3). UO2(NO3)2·6H2O aqueous solution (0.5 M; 200 μL, 0.1 mmol) and 1 M AgNO3 aqueous solution (100 μL, 0.1 mmol) were added to a suspension of H-3-MCPCA (0.056 g, 0.2 mmol) in water (1 mL) in a stainless steel bomb. After it was treated with ammonium hydroxide (10 μL), the mixture was sealed, kept at 150 °C for 48 h, and cooled to room temperature. Light yellow block crystals of 2 and yellowish-green prismatic crystals of 3, accompanied by a certain amount of unknown white crystals, were produced. The final crystals were filtered off, rinsed with water, and subjected to air-drying at room temperature. UO2Ag(OH)(PCA)2 (U−Ag-PCA) and (UO2)Ag2(OH)(H2O)2(PCA)4 (4). UO2(NO3)2·6H2O aqueous solution (0.5 M; 200 μL, 0.1 mmol) and 1 M AgNO3 aqueous solution (100 μL, 0.1 mmol) were added to a suspension of H-PCA (0.056 g, 0.2 mmol) in water (1 mL) in a stainless steel bomb. After it was treated with ammonium hydroxide (10 μL), the mixture was sealed, kept at 150 °C for 48 h, and cooled to room temperature. Known yellow block crystals of [UO2Ag(OH)(PCA)2],29 namely, as U−Ag-PCA here, accompanied by a small amount of smallsize needlelike yellow crystals of 4 were produced. The final crystal products were filtered off, rinsed with ultrapure water and ethanol, and subjected to air-drying at room temperature. X-ray Single-Crystal Structure Determination. X-ray diffraction data for 1−4 were all collected on an Agilent SuperNova X-ray CCD diffractometer with a Mo Kα X-ray source (λ = 0.710 73 Å) (for 1−3) or Cu Kα X-ray source (λ = 1.541 84 Å) (for 4) at room temperature. Standard Agilent Crysalis software was used for the determination of the unit cells and data collection control. All the crystal structures were solved by means of direct methods (SHELXS-9738) and refined with full-matrix least-squares on SHELXL-2014.38,39 All non-hydrogen atoms were refined with anisotropic displacement parameters. The carbon-

a (a) Different halogenations modes (2,6-positions and 3,5-positions) of multi-functional isonicotinic acid derivates with different binding modes: 2,6-positions, the pyridine moiety for binding with silver ion and carboxyl group only preferring to binding uranyl ion; 3,5positions, the pyridine moiety for binding with silver ion and carboxyl group binding with both uranyl ion and silver ion. (b) Three types of isonicotinic acid ligands with different halogenation patterns at the ortho positions of carboxyl group used in this work: H-3,5-DCPCA, H-3-MCPCA, and H-PCA.

adjacent coordinating groups with actinide ions and silver ions. In the case of U−Ag-2,6-DCPCA, halogenation at ortho positions of nitrogen atom on pyridyl ring of isonicotinate (i.e., 2,6-substituted) mainly exerts steric hindrance to the space room around nitrogen and damatically changes coordination behaviors of isonicotinate ligand. Along this line, it can be expected that, if halogen substitution changes from ortho positions of nitrogen atom (i.e., 2,6-substituted) to ortho positions of carboxyl group (i.e., 3,5-substituted) on pyridyl ring of isonicotinate, the conformation of carboxyl group and subsequently its coordination behavior with metal ions will be significantly altered, since there is strong repulsion force from halogen atoms. Herein, we are still devoted to the syntheses of heterometallic uranyl−silver compounds from different isonicotinate precursors with varying halogenation patterns so as to explore the effect of halogen atoms substituted at ortho positions of carboxyl group on the hydrothermal assembly of isonicotinate ligand with uranyl and silver ions. In this work, four new heterometallic uranyl−silver compounds 1-4, were synthesized from two isonicotinic acids with ortho chlorination of carboxyl group, 3,5-dichloroisonicotinic acid (H-3,5-DCPCA, the prefix of “H” means the acid form with a proton), and 3-chloroisonicotinic acid (H-3-MCPCA), as well as chlorine-free isonicotinic acid (H-PCA), respectively (Scheme 1b). Interestingly, compound 1 displays a heterometallic threedimensional (3D) framework through the connection of 3,5DCPCA and in situ-formed 3,5-dichloropyridine (3,5-DCPy) with the aid of multiple argentophilic interactions, while compounds 2 and 3 are heterometallic 3D reticular frameworks from 3-MCPCA based on highly coordinated silver nodes. To be noticed, highly coordinated silver ions, among which carboxyl groups of isonicotinate are the biggest contributors, play a vital role in constructing these intriguing heterometallic uranyl−silver 3D frameworks. Detailed structural analysis reveals that, as expected, the inclination of the carboxyl group of isonicotinate driven by large steric hindrance from bulky chlorine atoms at its B

DOI: 10.1021/acs.inorgchem.8b00402 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Table 1. Crystal Data and Structure Refinement for Compounds 1, 2, 3, and 4 formula formula weight crystal system space group a, Å b, Å c, Å α, deg β, deg γ, deg V, Å3 Z T, K Dc, g/cm3 μ (mm−1) F(000) θ (min, max) [deg] R1, wR2 [I ≥ 2σ(I)] R1, wR2 (all data) a

1

2

3

4

C46H18N8O14Cl16Ag4U 2143.39 monoclinic I2/m 11.5183(3) 18.1238(3) 14.8874(5) 90 99.620(3) 90 3064.12(14) 2 293(2) 2.323 4.656a 2028 3.060, 25.123 0.0294, 0.0561 0.0382, 0.0614

C18H9N3O8Cl3AgU 847.53 monoclinic P21/c 7.4731(3) 18.9035(9) 15.9409(6) 90 96.236(2) 90 2238.61(16) 4 298(2) 2.515 8.510a 1568 2.946, 27.555 0.0194, 0.0433 0.0226, 0.0444

C24H12N4O10Cl4Ag2U 1111.95 triclinic P1̅ 7.2831(4) 9.4767(6) 11.4136(7) 89.971(2) 83.977(2) 80.849(2) 773.34(8) 1 297(2) 2.388 6.882a 518 2.845, 27.101 0.0164, 0.0399 0.0166, 0.0401

C24H16N4O13Ag2U 1022.18 monoclinic C2/c 12.6438(17) 17.6395(18) 12.524(2) 90 103.146(16) 90 2720.0(7) 4 293(2) 2.496 28.708b 1912 4.379, 67.061 0.1001, 0.2854 0.1198, 0.3016

Mo Kα (λ = 0.710 73 Å). bCu Kα (λ = 1.541 84 Å).

Figure 1. (a) The asymmetric unit of 1; (b) the whole coordination modes of U1, Ag1, and Ag2; (c−e) the local coordination sphere of uranium and silver atoms: U1(c), Ag1 (d), and Ag2 (e).

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bound hydrogen atoms were placed at calculated positions, and all hydrogen atoms were treated as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. It should be mentioned that large residual density around U1, Ag1 as well as O1, O4, and O7 are observed, which might be attributed to weak diffraction of small-size crystals of 4. Crystallographic data and refinement details of all these three compounds are given in Table 1. Crystallographic data for all the structures in this paper were deposited with the Cambridge Crystallographic Data Centre as supplementary publication Nos. CCDC 1026413 (1), CCDC 1534275 (2), CCDC 1552331 (3), and CCDC 1026414 (4).

RESULTS AND DISCUSSION

Structural Description. Crystal Structure of (UO2)Ag4(3,5DCPCA)6(3,5-DCPy)2 (1). Compound 1 was synthesized from the hydrothermal reactions of uranyl nitrate hexahydrate and H-3,5DCPCA in the presence of silver nitrate and was isolated in pure phase (Figure S1). It crystallizes in the I2/m monoclinic system and contains four different types of components: uranyl ion, silver ion, 3,5-DCPCA linker, and in situ-formed 3,5-DCPy in its asymmetric unit (Figure 1a). The only uranium node (U1, Figure 1b), which locates at both centers of a C2 axis and a symmetry plane, is coordinated by four symmetrically equivalent C

DOI: 10.1021/acs.inorgchem.8b00402 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry Table 2. Selected Bond Distances (Å) of U−O Bonds and Bond Angles (deg) of [OUO] in Compounds 1−4 1 U(1)−O(3) O(3)−U(1)−O(3a) Ag(1)−N(6) Ag(1)−O(1) Ag(2)−O(4)

1.746(5) 180.0(0) 2.278(5) 2.433(3) 2.442(5)

U(1)−O(1) U(1)−O(3) U(1)−O(5) U(1)−O(7) Ag(1)−O(2) Ag(1)−O(8) Ag(1)−N(3)

1.755(2) 2.472(2) 2.339(2) 2.324(2) 2.634(2) 2.284(2) 2.260(2)

U(1)−O(1) U(1)−O(3) O(1)−U(1)−O(1a) Ag(1)−O(1) Ag(1)−O(5) Ag(1)−N(2)

1.766(2) 2.523(2) 180.0(0) 2.826(2) 2.258(2) 2.241(2)

U(1)−O(1) U(1)−O(4) Ag(1)−O(6) Ag(1)−O(7) Ag(1)−N(2)

1.738(2) 2.281(2) 2.490(2) 2.052(2) 2.20(2)

U(1)−O(2)

2.308(3)

Ag(1)−N(7) Ag(2)−N(3) Ag(2)−O(5)

2.300(6) 2.261(3) 2.608(5)

U(1)−O(2) U(1)−O(4) U(1)−O(6) O(1)−U(1)−O(2) Ag(1)−O(3) Ag(1)−N(1)

1.768(2) 2.469(2) 2.385(2) 177.2(1) 2.688(2) 2.407(3)

U(1)−O(2) U(1)−O(4)

2.551(2) 2.375(2)

Ag(1)−O(2) Ag(1)−N(1)

2.717(2) 2.472(2)

U(1)−O(2) O(1)−U(1)−O(1a) Ag(1)−O(6a) Ag(1)−N(1)

2.321(2) 179.3(8) 2.83(2) 2.24(2)

2

3

Figure 3. Monofunctional 3,5-DCPy linker promotes the formation of double-H-like chain of 1 with two cutoff terminals, which further extend to a wavelike layered structure and finally a 3D framework.

group binding to uranyl center (Ag(1)−O(1): 2.433(3) Å) and further with two pyridyl groups from a 3,5-DCPCA (N6) and 3,5-DCPy (N7) linker to form a square geometry (Ag(1)−N(6): 2.278(5) Å; (Ag(1)−N(7): 2.300(6) Å). Unlike Ag1, the silver ions, namely, as Ag2 always occur in pairs, which chelate by two sets of η2-carboxyl groups (O4 and O5) of 3,5-DCPCA linkers from opposite directions (Ag(2)−O(4): 2.442(5) Å; (Ag(2)− O(5): 2.608(5) Å), each of which further coordinates with two equivalent pyridyl groups (N3) in the vertical direction to complete its coordination sphere. Notably, the interaction between the Ag2 ions in pair here belongs to a typical argentophilicity double supported by carboxylate O, O-bridging (Figure 2, d2[Ag2···Ag2]: 2.891(1) Å).40 In spite of wide participation of silver in the coordination with pyridyl or carboxyl groups of 3,5-DCPCA linker, the monofunc-

4

η1-carboxyl group (O2) of 3,5-DCPCA linker (U1−O2: 2.308(3) Å, Table 2) as well as two axial oxygen (O3) atoms (U1−O3: 1.746(5) Å, Table 2) and finally forms a tetragonal bipyramid geometry (U1 in Figure 1c). Two kinds of silver ions with different coordination modes, Ag1 and Ag2, are found in 1. The Ag1 ion coordinates with the other oxygen atom of carboxyl

Figure 2. (a) The 3D framework of 1 packed from the wavelike layered structures; (b) square cavities found in the reticular framework of 1; (c) the local structure of the 3D framework showing the argentophilic interactions between adjacent layers corresponding to a linear tetrameric silver (Ag1···Ag2··· Ag2···Ag1) cluster (d1[Ag1···Ag2] = 3.060(1) Å; d2[Ag2···Ag2] = 2.891(1) Å). D

DOI: 10.1021/acs.inorgchem.8b00402 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Figure 4. (a) The asymmetric unit of 2; (b) the whole coordination modes of U1and Ag1; (c) the local coordination sphere of U1; (d) the local coordination sphere of Ag1.

Figure 5. (a, b) The uranyl dimer surrounded by eight silver ions from different directions in 2 viewed from b axis (a) and a axis (b); (c, d) the 2D network extended along the ac plane viewed from b axis (c) and a axis (d) (polyhedron in orange or yellow color, uranyl polyhedron; polyhedron in bright green or light blue, silver polyhedron; stick in orange color, 3-MCPCA linker around the modeled uranyl dimer; stick in light blue color, other 3MCPCA linkers of the 2D network); (e, f) the 3D framework of 2 viewed from b axis (e) and a axis (f) (polyhedron in orange or yellow color, uranyl polyhedron; polyhedron in dark green, silver polyhedron).

tional 3,5-DCPy linker cuts off two possible growth pathways for 1 by binding to the Ag1 ions, finally resulting in a wavelike layered structure (Figure S2). Furthermore, these bumpy layered structures pack with each other to construct a 3D framework (Figures 2a,b and 3). Detailed analysis on the local structure of the 3D framework reveals that another argentophilic interaction

between Ag1 and Ag2 from adjacent layers (Figure 3c, d1[Ag1··· Ag2]: 3.060(1) Å) plays a vital role for its stabilization. Actually, the superposition of the above two types of argentophilic interactions leads to a special linear tetrameric silver (Ag1··· Ag2···Ag2···Ag1) cluster with enhanced argentophilicity. E

DOI: 10.1021/acs.inorgchem.8b00402 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 6. (a) The asymmetric unit of 3; (b) the whole coordination modes of U1and Ag1; (c) the local coordination sphere of U1; (d) the local coordination sphere of Ag1.

Figure 7. High connectivity of silver ion promotes the uranyl building unit to extend from three directions and results in a heterometallic uranyl−silver 3D framework: (a) 1D chain linked by the wide coordination of O donors around uranyl nodes with silver centers viewed from b axis; (b) 2D sheet by the coordination of N donors of pyridyl groups on both sides with silver centers from adjacent chains viewed from b axis; (c) 2D sheet viewed from a axis; (d) heterometallic uranyl−silver 3D framework with two kinds of square channels in sizes of 7.8 × 6.4 Å and 3.0 × 6.9 Å cross-linked by another set of Ag−N bonds along b axis.

Crystal Structure of (UO2)Ag(3-MCPCA)3(2) and (UO2)Ag2(3-MCPCA)4 (3). When the synthesis started from a monochloro-substituted isonicotinic acid precursor, H-3MCPCA, two heterometallic uranyl−organic compounds 2 and 3 were produced. The crystal structure of 2, which crystallizes in the P21/c monoclinic system, contains one uranyl ion, one silver ion, and three 3-MCPCA linkers (Figure 4a). The uranyl center exists as a carboxylate O,O-bridging dimer (O5 and

O6; U(1)−O(5): 2.339(2) Å; U(1)−O(6): 2.385(2) Å), and the coordination sphere of each uranyl in the dimer is further occupied by another two linkers, namely, an η2-carboxyl group (O3 and O4; U(1)−O(3): 2.472(2) Å; U(1)−O(4): 2.469(2) Å) and an η1-carboxyl group (O7; U(1)−O(7): 2.324(2) Å), leading to a pentagonal bipyramid geometry (Figure 4b,c). Unlike the case of 1, only one kind of silver ion with a tetragonalpyramid coordination environment is found in 2. Specially, the F

DOI: 10.1021/acs.inorgchem.8b00402 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 8. (a) The asymmetric unit of 4; (b) the whole coordination modes of U1and Ag1; (c) the local coordination sphere of U1; (d) the local coordination sphere of Ag1; (e) the extended 1D chain of 4 viewed from the right above; (f) 1D chain of 4 viewed from the side face.

suspended oxygen atom (O8; Ag(1)−O(8): 2.284(2) Å) of η1carboxyl group coordinated to uranyl center and one axial oxygen atom (O2; Ag(1)−O(2): 2.634(2) Å) as well as one oxygen (O3; Ag(1)−O(3): 2.688(2) Å) from the η2-carboxyl group belonging to the coordination sphere of the adjacent uranyl dimer all contributed to the formation of tetragonal-pyramid geometry for the Ag1 node (Figure 4b,d). Actually, the inclusion of axial oxygen atom of uranyl center in the coordination sphere of Ag1 could be thought of as a special type of cation−cation interaction (CCI) based on the uranyl and heterometallic nodes.22,41−43 Besides, another two 3-MCPCA linkers also bind to Ag1 through the N-donors of pyridyl groups (N1 and N3; Ag(1)−N(1): 2.407(3) Å; Ag(1)−N(3): 2.260(2) Å). Interestingly, each uranyl dimer is surrounded by eight silver ions from different directions, and these highly coordinated silver ions help to weave a 3D framework through their cross-linking capacity (Figure 5). Another crystal phase among the hydrothermal products of uranyl and H-3-MCPCA in the presence of silver ion is compound 3. It crystallizes in the P1̅ monoclinic system and contains both uranyl and silver ions in its structure (Figure 6a). Unlike the carboxylate-bridging uranyl dimer in 2, an eightcoordinated centrosymmetric monomeric uranyl center containing two η2-carboxyl groups (O2 and O3; U(1)−O(2): 2.551(2) Å; U(1)−O(3): 2.523(2) Å) and two η1-carboxyl groups (O4; U(1)−O(4): 2.375(2)) is observed in 3 (Figure 6b,c). Although there is large difference in uranyl species and coordination pattern for 2 and 3, the coordination sphere of each silver ion for them is nearly identical (Figure 6b,d), that is, tetragonal-pyramid coordination environment geometry with three kinds of oxygen atoms (O1, O2 and O5; Ag(1)−O(1): 2.826(2) Å; Ag(1)−O(2): 2.717(2) Å; Ag(1)−O(5): 2.258(2) Å) and two N-donor atoms from different 3-MCPCA linkers (N1 and N2; Ag(1)−N(1): 2.472(2) Å; Ag(1)−N(2): 2.241(2) Å). Again similar to the case of 2, high connectivity of silver ion in 3 also promotes the uranyl building unit to extend from three directions and results in a heterometallic uranyl−silver 3D

framework (Figure 7). Actually, the wide coordination of O donors (the suspended O5 atom of η1-carboxyl group, the axial O1 atom, and the O2 atom of the η2-carboxyl group) around uranyl nodes with silver centers leads to a one-dimensional (1D) chain (Figure 7a), which further assembles into a twodimensional (2D) sheet by the coordination of N-donors of pyridyl groups on both sides with silver centers from adjacent chains (Figure 7b). Furthermore, another set of Ag−N bonds along b axis connects all the 2D sheets to form a heterometallic uranyl−silver 3D framework with two kinds of square channels in sizes of 7.8 × 6.4 Å and 3.0 × 6.9 Å (Figure 7c,d). Notice that, since the axial oxygen atoms participate the coordination of silver ion through the [UO−Ag] bond and weaken the strengths of UO bonds, the IR stretching ribbons of UO bonds in 2 and 3 both shift to lower wave numbers compared with that of 1 (see Figure S3. The IR stretching ribbons for different compounds: 1, 932 cm−1; 2, 910 cm−1; 3, 911 cm−1; U−Ag-PCA, 918 cm−1). Crystal Structure of (UO2)Ag2(OH)(H2O)2(PCA)4 (4). Compound 4 is a minor product accompanied by large amount of known yellow block crystals, U−Ag-PCA,29 when starting from nonchloride isonicotinic acid (H-PCA). Although both uranyl and silver nodes are present in the asymmetric unit of 4 (Figure 8a), their coordination spheres are totally different than that of U−Ag-PCA (Figure S4). The uranyl center is coordinated by four η1-carboxyl groups of PCA linkers (two O2 atoms and two O4 atoms; U(1)−O(2): 2.321(2) Å; U(1)−O(4): 2.281(2) Å), and it affords a final tetragonal pyramid, which is similar to the uranyl sphere found in 1 (Figure 8b,c). Moreover, similar to Ag2 in 1, the Ag1 node in 4 also always occurs in a pair with Ag−Ag distance of 3.283(4) Å. However, the coordination environment of Ag1 is slightly different, each of which is coordinated by three O donors (one O7 atom, two O6 atoms; Ag(1)−O(7): 2.052(2) Å; Ag(1)−O(6): 2.490(2) Å; Ag(1)−O(6a): 2.83(2) Å) (Figure 8b,d). Bond valence sum (BVS) analysis44,45 of these three oxygen atoms reveals that the bond valence for each Ag1−O7 bond is 0.567, while those for Ag1−O6 bonds are 0.0174 and G

DOI: 10.1021/acs.inorgchem.8b00402 Inorg. Chem. XXXX, XXX, XXX−XXX

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Table 3. A Comparison between Uranyl Compounds with Single UO22+ and Those with Both UO22+/Ag+, where Different Isonicotinic Acids Were Used as the Reaction Precursors

a

2-MHPCA:37 2-hydroxyisonicotinate.

of hydroxyl group (OH), while the BVS for O6 is 0.0243 corresponding to a water molecule (H2O). The main difference between 1 and 4 is the lack of silver ions coordinated with the other oxygen atom (O3 or O5) of η1-carboxyl group around uranyl center, which finally leads to a 1D chain (Figure 8e,f), not 3D framework as 1. The Role of Silver Ion in Constructing Heterometallic Uranyl−Organic Compounds. The isonicotinate skeleton is used as an organic linker here on account of its bearing of bifunctional groups (carboxyl and pyridinyl), which have the potential capacity to coordinate with both uranyl and transitionmetal center (such as silver ion) simultaneously. Actually, the introduction of a second nonuranium metal center in heterometallic uranyl−organic compounds18,29 distinguishes them from uranyl−organic compounds with only uranyl nodes.37,46−48 Hence, the comparison between heterometallic uranyl−silver and simple uranyl−organic compounds was conducted to figure out the role of silver ion (Table 3). Note

Scheme 2. Different Coordination Patterns of Carboxyl Groups in 1−4: (a) η1-U; (b) η2-U; (c) μ2: η1-U, η1-U; (d) μ2: η1-U, η1-Ag; (e) μ3: η2-U, η1-Ag; (f) μ2: η1-Ag, η1-Ag

0.069. The BVS for Ag1 is 0.81, which is consistent with its usual AgI oxidation state. The BVS for O7 is 1.134, indicating its nature H

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Table 4. Dihedral Angles (θ, deg) between the Pyridyl Plane and the Adjacent Carboxyl-Containing Plane for the Ligands and the Corresponding Heterometallic Uranyl−Silver Compounds

The role of silver ion is also reflected in its participation in the coordination with carboxyl group, which enriches coordination patterns of carboxyl groups. As shown in Scheme 2, besides three kinds of uranyl-involved coordination modes ((a) η1-U; (b) η2U; (c) μ2: η1-U, η1-U), the presence of silver in the hydrothermal system brings in another three new coordination modes ((d) μ2: η1-U, η1-Ag; (e) μ3: η2-U, η1-Ag; (f) μ2: η1-Ag, η1-Ag), where silver ion coordinates to carboxyl group together with uranyl or solely by itself. The Effect of Stepwise ortho Chlorination of Carboxyl Group on Structural Variance. The most interesting issue is how ortho chlorination of carboxyl group affects the assembly behavior of isonicotinic acid with uranyl in the presence of silver ion. Therefore, we made a detailed analysis of molecular structures of H-3,5-DCPCA,37 H-3-MCPCA,49 H-PCA,50 H2,6-DCPCA,51 and their corresponding heterometallic uranyl− silver compounds, mainly focusing on the dihedral angles (θ) between the pyridyl plane and the adjacent carboxyl-containing plane (Table 4). The carboxylic acids without any ortho chlorination of carboxyl groups, that is, H-PCA or H-2,6DCPCA, show a small deflection angle of 12.6(1)°−18.9(1)°. The ortho chlorination at one side of carboxyl group for H-3MCPCA induces a larger deflection angle of 33.3(5)° because of

that, although several uranyl complexes with isonicotinic acid have been reported, those cases incorporating competing anions (such as NO3−, ReO4−, or TcO4−) in the coordination sphere of uranium center are excluded from discussion for the sake of convenience, and only uranyl isonicotinate compounds with single isonicotinate ligand as well as hydro/water groups are included in Table 3. The distinctive difference of uranyl building units in these two series of uranyl complexes reveals that the additional silver ion, whether it competes with uranyl in pyridinyl or carboxyl coordination or not, has a significant effect on uranyl species. For example, on the one side, for 3,5-DCPCA ligand (compound 1), silver ion participates in both the pyridinyl and carboxyl coordination and subsequently leads to a transformation of uranyl sphere from a pentagonal bipyramid geometry to a tetragonal bipyramid geometry. On the other side, though silver ion does not compete with uranyl in carboxyl coordination in 4 with chlorine-free PCA ligand (Figure S5), uranyl sphere also undergoes a significant change compared to that without silver, just like the case of 3,5-DCPCA ligand. The mechanism for Ag+-based regulation might be that, in the presence of silver ion, new uranyl building units more favorable to coordinate with silver ion are preferred than those ones found in the simple uranyl-only system. I

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Figure 9. Stepwise ortho chlorination of carboxyl groups promotes them to deviate from the pyridinyl ring and avoids the potential repulsion from adjacent atoms of pyridinyl ring, providing more available space for binding to incoming silver ions after coordination with uranyl center.

Table 5. Dihedral Angles (φ) between the Plane Belonging to η1-COO Group and the Equatorial Plane of Uranyl Center It Coordinates with

a

Tetragonal bipyramid. bPentagonal bipyramid. cHexagonal bipyramid.

be in a near-vertical orientation (θ = 77.8(2)°). The deflection angles found in heterometallic uranyl−silver compounds do not show any significant change compared to those of the

repulsion force from the neighboring bulky chlorine atom, while simultaneous ortho chlorination at both sides for H-3,5-DCPCA generates much stronger repulsion, making the carboxyl group J

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Luminescence Properties. Fluorescence spectra under excitation at a wavelength of 420 nm were recorded for compound 1 with 3,5-DCPCA ligand (pure 2, 3, and 4 could not be isolated in sufficient yields). As a control, the uranyl fluorescence for U−Ag-2,6-DCPCA and U−Ag-PCA were also given in Figure 10. Unlike the fluorescence characteristic peaks of U−Ag-2,6-DCPCA at 495 (s), 517 (s), 541 (m), 567 (m), and 626 (w) nm corresponding to the S11 → S00 and S10 → S0ν (ν = 0−4) electronic transitions,52 the fluorescence spectrum of compound 1 displays quenching of uranyl luminescence and only three weak peaks at 498 (w), 515 (w), and 534 (w) nm. Theoretically, originated from electronic transitions between the lowest unoccupied molecular orbital (LUMO) 5f nonbonding orbitals of uranyl center and the highest occupied molecular orbital (HOMO) hybrid σ-bonding orbital of U−O bond, referred to as UO axial ligand-to-metal charge transfer (LMCT) bands,53,54 the fluorescence of the uranyl cation features five or six vibronic peaks in the range from 450 to 650 nm. Considering that silver ion directly coordinates to the carboxyl group around sixfold coordinated uranyl center, the quenching fluorescence found with 1 should be largely related to the competing coordination of silver ion. On the one hand, similar silver ion-induced quenching phenomenon occurs for U− Ag-PCA (Figure 10). On the other hand, a red shift has been observed for the weak vibronic peaks of 1 relative to those of U− Ag-PCA, which is certainly due to their distinct uranyl coordination modes.20,53,55

Figure 10. Fluorescence spectrum of compound 1 under excitation at a wavelength of 420 nm with those of U−Ag-2,6-DCPCA and U−AgPCA as comparison.

corresponding simple carboxylic acids on the whole, and similarly heterometallic uranyl−silver compounds from H-3MCPCA and H-3, 5-DCPCA with ortho chlorination of carboxyl group display larger deflection angles. Moreover, it is interesting to find that silver ions are without exception excluded from the coordination spheres of carboxyl groups for all the heterometallic uranyl−silver compounds from H-PCA or H-2,6-DCPCA without ortho chlorination of carboxyl group (located at top-right corner of Table 4), but carboxyl groups in 1, 2, and 3 from H-3-MCPCA and H-3,5-DCPCA with ortho chlorination of carboxyl group prefer to coordinate with both uranyl and silver ions simultaneously (located at bottomleft corner of Table 4). The extraordinary preference of carboxyl groups for silver ion in 1, 2, and 3 might be related to special offplane geometric configuration of ortho chlorinated isonicotinate ligands, which avoids the potential repulsion from adjacent atoms of pyridinyl ring and provides more available space for binding to incoming silver ions after coordination with uranyl center (Figure 9). On the contrary, steric hindrance still exists for HPCA or H-2,6-DCPCA without ortho chlorination of carboxyl group, preventing uranyl-coordinated carboxyl groups from further binding of silver ions. Actually, for ease of binding of silver ion, carboxyl groups around uranyl centers are specially orientated (Figure S6). Furthermore, Table 5 shows the detailed dihedral angles (φ) between the plane belonging to η1-COO group and the equatorial plane of uranyl center it coordinates with for all the heterometallic uranyl−silver compounds. On the one hand, for uranyl center in T-type (tetragonal bipyramid), the η1-COO plane in 1 is nearly parallel with the equatorial plane of uranyl center (φ = 21.1(2)°), ensuring simultaneous coordination of uranyl and silver ions, whereas a remarkable departure from uranyl equatorial plane (φ = 61.8(1)°) rules out the possibility of silver ions. On the other hand, the carboxyl plane is nearly perpendicular to the equatorial plane of uranyl center (φ = 76.0(2)° and 81.4(2)°) in P-type (pentagonal bipyramid) or Htype (hexagonal bipyramid) of 2 or 3, while much smaller deflection angles (φ = 27.4(6)° and 37.4(5)°) can be found in U−Ag-PCA29 or U−Ag-2,6-DCPCA.18 Certainly vice versa, the participation of silver ion into the coordination sphere of carboxyl groups also contributes more or less to its special orientation, which can serve as another evidence of the important role of silver ions in the assembly of heterometallic uranyl complexes.

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CONCLUSIONS In this work, the syntheses and characterizations of four new heterometallic uranyl−silver compounds, 1−4, from isonicotinic acid derivatives with a stepwise ortho chlorination of carboxyl group, that is, isonicotinic acid (H-PCA), 3-chloroisonicotinic acid (H-3-MCPCA), and 3,5-dichloroisonicotinic acid (H-3,5DCPCA, have been reported. It is found that large steric hindrance from bulky chlorine atoms at ortho positions of carboxyl group promotes its departure from the pyridine plane progressively and helps it to participate in the coordination sphere of highly coordinated silver ion, leading to the formation of 1, 2, and 3 with intriguing heterometallic uranyl−silver 3D frameworks. These interesting heterometallic uranyl−silver frameworks enriches the family of actinide-based inorganic− organic hybrid materials and, most importantly, offer an effective approach to tune the structures of heterometallic uranyl−silver compounds via a stepwise ortho chlorination strategy.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00402. Typical figures including PXRD patterns, IR spectra, and crystal structure for some compounds in 1−4 are included (PDF) Accession Codes

CCDC 1026413−1026414, 1534275, and 1552331 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. K

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Lei Mei: 0000-0002-2926-7265 Zhi-hui Zhang: 0000-0002-8744-7897 Wei-qun Shi: 0000-0001-9929-9732 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are thankful for the support of this work by the National Natural Science Foundation of China (21671191, 21577144, and 11405186) and the Major Program of National Natural Science Foundation of China (No.21790373). The Science Challenge Project (JCKY2016212A504) is also acknowledged. We appreciate the help from Prof. Dr. Sun and Dr. L. Zhang for Xray single-crystal measurements.

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M

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