Various of Silver Phosphinate Inorganic Architectures in Three

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Various of Silver Phosphinate Inorganic Architectures in ThreeDimensional Frameworks with Argentophilic Interactions Meng-Qin He, Ye Xu, Ming-Xing Li, Min Shao, and Zhao-Xi Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00111 • Publication Date (Web): 16 Mar 2019 Downloaded from http://pubs.acs.org on March 17, 2019

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Crystal Growth & Design

Various of Silver Phosphinate Inorganic Architectures in Three-Dimensional Frameworks with Argentophilic Interactions Meng-Qin He, † Ye Xu, † Ming-Xing Li, *† Min Shao, ‡ and Zhao-Xi Wang *† Department of Chemistry, Center for Supramolecular Chemistry and Catalysis, Innovative Drug Research Center, Shanghai University, Shanghai 200444, People’s Republic of China ‡ Laboratory for Microstructures, Shanghai University, Shanghai 200444, People’s Republic of China †

ABSTRACT: Three silver compounds with the formulas: [Ag2(HL1)] (1), [Ag10(L2)2(H2O)1.25] (2) and [Ag5(L3)]·1.5H2O (3) were obtained by self-assembly of silver nitrate with 4,4'-phosphinicobis-dibenzoic acid (H3L1), 4,4'-phosphinicobis-diisophthalic acid (H5L2), and 2,2'-phosphinicobis-diisophthalic acid (H5L3) under hydrothermal condition. The structures of these compounds were confirmed by various characterization methods. Both 1 and 2 crystallize in P21/n space group and present three-dimensional (3D) frameworks, which contain sliver phosphinate inorganic chain or sheet formed by Ag-Ag interactions. Whereas, compound 3 is in C2/c space group and also displays a 3D silver-organic architecture. The open-framework contains narrow channels along the caxis with an opening of 0.26  0.32 nm2. The intriguing feature of the structure is emergence of a 3D inorganic skeleton in 3, which struts the whole framework. The 3D inorganic skeleton is generated from silver phosphinite chain connected by strong Ag−Ag interactions. At room temperature, the compounds exhibit blue photoluminescence.

INTRODUCTION The rational design and synthesis of metal phosphinates has garnered great attention from many researchers relating to chemistry and materials science due to their application in various fields. 1-10 For instance, a cuboidal tetranuclear manganese constructed with diphenylphosphinic acid can act as an oxygen evolving complex for water oxidation in photosystem II. 2 A cobalt compound built with a racemic phosphonate ligand can exhibit both polarity and ferromagnetism. 11 Phosphinate anion and its derivatives are a class of good ligands to prepare coordination polymers. 12,13 Firstly, phosphinate anion has strong coordination bonds to metals resulting the product stable against hydrolysis. 14 On the other hand, the derivatives of phosphinate with its coordination sites offer a high likelihood for construction of multi-dimensional architectures. 15,16 In a word, metal phosphinates are very important for their unique physical and chemical properties. Recently, we have presented that 2,2'-phosphinicodibenzoic acid is useful ligand to connect metal ions into different skeletons. 17-20 In particular, the preparation of Ag(I) compounds has aroused great interesting, since Ag(I) possesses d10 electronic configuration21-24 and the incorporation of d10 metal ions has an important influence on the photoluminescent emissions. 25,26 Also, the Ag(I) ion often displays a highly versatile and irregular coordination number and geometry, which may lead to the discovery of new

architectures. 27-30 As a matter of fact, we found that 2,2'phosphinico-dibenzoic acid reacts with silver nitrate to assemble two unusual coordination polymers: a symmetric 2D network built by strong silver(I)–aromatic interaction, in the case of low metal–ligand ratio, and a noncentrosymmetric sheet, in the case of increasing metal–ligand ratio. 17

Scheme 1. Ligands of H3L1, H5L2 and H5L3.

To develop the systems of 2,2'-phosphinico-dibenzoic acid with silver ion for resulting 3D networks, now we designed and synthesized three new functionalized phosphinic acids: namely, 4,4'-phosphinicobis-dibenzoic acid (H3L1), 4,4'phosphinicobis-diisophthalic acid (H5L2), and 2,2'phosphinicobis-diisophthalic acid (H5L3) (scheme 1), which

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possess carboxylate and phosphinate oxygen atoms to coordinate metal ions in versatile coordination modes. In this work, we employed these phosphinic acids as ligand to react with silver nitrate and successfully prepared three 3D coordination frameworks. It is interesting that the frameworks contain various of silver phosphinate inorganic architectures from 1D to 3D respectively. Hereon, we report the preparation, crystal structures and luminescent properties of the three compounds [Ag2(HL1)] (1), [Ag10(L2)2(H2O)1.25] (2) and [Ag5(L3)]·1.5H2O (3) in details. EXPERIMENTAL SECTION Materials and Methods. All reagents were commercial sources of analytical grade. The ligands 4,4'-phosphinicobisdibenzoic acid (H3L1), 4,4'-phosphinicobis-diisophthalic acid (H5L2), and 2,2'-phosphinicobis-diisophthalic acid (H5L3) were prepared as previously described. 31-33 C and H analyses were performed on a Vario EL-III elemental analyzer. IR spectra were carried on a Nicolet Avatar A370 spectrophotometer in the range of 4000- 400 cm−1 with KBr pellets. PXRD were recorded on a Rigaku D/ Max-2200 diffractometer using Cu Kα radiation (λ = 1.5406 Å) over the 2θ range from 5 to 50°. On a Netzsch STA 449C thermal analyzer, TGA were performed in nitrogen atmosphere at a 10 ºC/min heating rate. Solid luminescent spectra were recorded on a Shimadzu RF5310 fluorescence spectrophotometer. Synthesis of [Ag2(HL1)] (1). Reaction of AgNO3 (0.9 mmol) and H3L1 (0.05 mmol) with 6 mL deionized water in a sealed autoclave at 120 ºC for 3 days. Colorless prism-shaped crystals of 1 were obtained in 79% yield based on H3L1. Elemental analysis calcd (%) for C14H9O6PAg2 (519.92): C, 32.34; H, 1.74. Found: C, 32.44; H, 1.63%. IR / cm-1 (KBr): 3452(m), 2831(m), 1685(s), 1531(s), 1371(s), 1292(s), 1109(s), 911(s), 854(m), 735(s), 591(s), 537 (m). Synthesis of [Ag10(L2)2(H2O)1.25] (2). The synthesis process was similar to 1. Prism-shaped colorless crystals of 2 were obtained in 88% yield based on H5L2. Elemental analysis calcd (%) for C128H58Ag40O85P8 (7518.30): C, 20.44; H, 0.78. Found: C, 20.51; H, 0.72%. IR / cm-1 (KBr): 3384(m), 1585(s), 1541(m), 1375(s), 1094(m), 992(m), 744(m). Synthesis of [Ag5(L3)]·1.5H2O (3). The prepartion of 3 was similar to 1. Block colorless crystals of 3 were obtained in 55% yield based on H5L3. Elemental analysis calcd (%) for C32H17Ag10O23P2 (1910.09): C, 20.12; H, 0.90 ； Found: C, 20.01; H, 0.84%. IR / cm-1 (KBr): 3360(m), 1514(s), 1370(s), 1123(m), 1007(m), 756(m), 702(m). X-ray Crystallography. Used a Bruker SMART APEX-II CCD diffractometer equipping graphite-monochromatized Mo Kα radiation (λ= 0.71073 Å) with φ- ω scan technique, Singlecrystal data for compounds 1−3 were collected. Data were reduced by Bruker SAINT package. with SADABS program, absorption correction was carried out. After solved by the direct methods, the structures were further refined using SHELXL program 34 on F2 by full-matrix least-squares for non-hydrogen atoms with anisotropy. H atoms were introduced in calculations using the riding model. Crystallographic data are listed in Table 1.

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Compounds

1

2

3

Formula

C14H9O6PAg2

C128H58Ag40O85P8

C32H17Ag10O23P2

Formula weight

519.92

7518.30

1910.09

Crystal system

Monoclinic

Monoclinic

Monoclinic

Space group

P21/n

P21/n

C2/c

a(Å)

12.939(3)

13.6562(12)

18.614(12)

b(Å)

5.7915(11)

18.6709(16)

15.510(10)

c(Å)

18.359(4)

15.7069(14)

15.713(10)

β(º)

90.967(2)

111.698(6)

120.814(6)

V (Å3)

1375.5(5)

3721.1(6)

3896(4)

Z

4

1

4

Dc (g cm-3)

2.511

3.347

3.256

F(000)

1000

3506

3572

GOF on F2

1.033

1.042

1.095

R1,wR2[I >2σ(I)]

0.0274, 0.0704

0.0326, 0.0767

0.0368, 0.0905

R1,wR2 (all data)

0.0309, 0.0727

0.0399, 0.0809

0.0403, 0.0931

RESULTS AND DISCUSSION Syntheses and IR spectra. We intend to explore the structural effect of carboxyphosphinate ligand geometry on the topology of silver(I) coordination polymers. Previously, we prepared one carboxyphosphinate ligand 2,2'-phosphinicodibenzoic acid and found that its silver(I) compounds show symmetric or noncentrosymmetric 2D architecture controlled by metal to ligand ratios.17 For this goal, we synthesized other three carboxyphosphinate ligands and modified their structures by varying the spacer unit (Scheme 1). In order to precisely estimate the influence of the geometry of ligands on the structure of the resultants, and to overcome other side effects of solvent, temperature and metal–ligand ratio, we have used the same condition as previous. The reactions of AgNO3 with H3L1, H5L2, and H5L3 ligands in a 9:1 molar ratio resulted in three new air- and moisture-stable compounds, which exhibit three dimensional polymeric structures with characterization by single crystal X-ray diffraction. In the infrared spectra of 1, 2 and 3 (Figure S1), it can be clearly observed that the strong characteristic band of P=O appears in the region of 1395 ~ 1014 cm-1 and the middle peaks of P–O appears in the region of 1050 ~ 850 cm-1.35-40 A strong peak of 1685 cm-1 in compound 1 indicated the presence of carboxylic acid group with proton. And multiple strong peak also appeared in the range of 1600 ~ 1500 cm-1, which proved that only one carboxyl group is deprotonated, which are in agreement with the crystal structure of 1. While in the IR spectra of 2 and 3, no significant characteristic peaks were found near 1700 cm-1. But there were particularly strong peaks near 1590 ~ 1514 cm-1 indicated that all carboxyl groups had been deprotonated.41-45

Table 1. Crystallographic Parameters and Refinement for 1-3.


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Figure 1. (a) Molecule of 1; (b) Coordination mode of (HL1)2ligand; (c) A 1D inorganic silver phosphinite chain along b-axis (blue stick: Ag−Ag interaction); (d) 3D framework. Hydrogen atoms are removed for clarity. Symmetry code: a: x, y+1, z; b: x+3/2, y+1/2, -z+1/2; c: -x+1, -y+1, -z; d: -x+1,-y,-z+1; e: x+1/2, y+3/2, z+1/2.

Structure of [Ag2(HL1)] (1). Compound 1 crystallizes in the monoclinic P21/n space group and shows a 3D stereoscopic structure. There are two Ag(I) ions and one partially deprotonated (HL1)2− anion in its asymmetric unit. As showed in Figure 1a, both Ag1 and Ag2 own four-coordinated oxygen atoms. Ag1 shows a very distorted tetrahedral geometry formed by oxygen atoms of three phosphinite and one carboxylate groups from four different ligands (HL1)2respectively. While, Ag2 exhibits an extremely distorted tetrahedron constructed by four oxygen atoms of two phosphinite and two carboxylate units from four ligands. The bond lengths of Ag−O fall in the range of 2.174(2)−2.560(2) Å (Table S1), coincided to those reported in silver(I) coordination compounds. 46-50 In compound 1, each (HL1)2links eight silver(I) ions (Figure 1b), which is very different from its Mn(II) compound. 51 It is noted that the phosphinite group behaves as a μ5-bridge and links five Ag(I) ions via two oxygen atoms. Via this binding mode, the phosphinite units concatenate silver ions into an inorganic silver phosphinite chain in the b direction. In the silver phosphinite chain, Ag−Ag interactions among the Ag atoms lead to form a zigzag chain (Figure 1c), which is different from the results in document. 52 The Ag−Ag contact of 3.308 Å are less than the sum of the van der Waals radii of two Ag atoms (3.44 Å).53 The weak argentophilic interaction are similar to the reported compounds.54 Furthermore, the silver phosphinite inorganic chain is extended to form a 3D framework with four adjacent chains by benzoic units (Figure 1d). Structure of [Ag10(L2)2(H2O)1.25] (2). Compound 2 is a 3D network and crystallizes in the monoclinic P21/n space group. As presented in Figure 2a, its asymmetric unit composes of two completely deprotonated ligands (L2)5-, ten distinct Ag(I) ions and one and a quarter terminal water ligand. As observed in compound 2, all silver ions exhibit three coordination geometries. Ag1 and Ag10 are linear centered by two oxygen atoms, respectively. Ag4, Ag5, Ag7, Ag8, and Ag9 are trigonal centers surrounded by three oxygen atoms from

phosphinite and carboxylate units respectively. The remaining Ag2, Ag3, and Ag6 are four-coordinated and present tetrahedrally coordinated geometries around by four oxygen atoms from water molecule, carboxylate and phosphinite groups respectively. All Ag−O distances are in the range of 2.145(4)−2.585(4) Å, identified with those in 1 (Table S1). In compound 2, there are two fully deprotonated (L2)5anions, which adopt complicated μ13-, and μ14- bridging coordination modes, (η1:η1-μ2)-(η2:η1-μ3) -(η2:η2-μ4)-(η2:η2-μ4)(η1:η1-μ2)-μ13 and (η1:η1-μ2)-(η2:η2-μ4)-(η3:η2-μ5)-(η1:η1-μ2) (η1:η1-μ2)-μ14 modes (Figure 2b-c), to connect fourteen, or thirteen silver ions, respectively. With those coordination modes, phosphinite units concatenate silver ions into an inorganic silver phosphinite chain along the a-axis. The neighboring silver phosphinite chains are connected by strong Ag−Ag interaction (Ag4−Ag5 2.9546(7) Å and Ag7−Ag8 2.9810(7) Å) leading to produce a 2D inorganic layer in ac plane (Figure 2d), which is similar to the reported compounds.52 Furthermore, the inorganic sheets are extended to form a 3D framework by isophthalic groups (Figure 2e).

Figure 2. (a) Molecular unit of 2; (b) and (c) Coordination modes of (L2)5- ligand; (d) 2D inorganic sheet in ac plane (aqua and blue stick: Ag−Ag interaction); (e) 3D framework. Hydrogen atoms are dislodged for clarity. Symmetry code: a: -x+2, -y, -z+1; b: x-1/2, y+1/2, z+1/2; c: -x+2, -y, -z; d: x-1/2, -y-1/2, z-1/2; e: x-1/2, y+1/2, z-1/2; f: -x+2, -y+1, -z+1; g: -x+3/2, y-1/2,-z+1/2; h: -x+2, y-1, -z ; i: -x+3/2, y+1/2 ; -z+1/2 ; j: -x+5/2, y+1/2, -z+1/2; k: x, y+1, z.

Structure of [Ag5(L3)]·1.5H2O (3). Compound 3 crystallizes in the monoclinic space group C2/c, and exhibits a 3D network. The repeating unit is composed of six



crystallographical silver(I) ions (Ag2 and Ag6 with 50% occupancy), and one completely deprotonated (L3)5- ligand, as well as 1.5 lattice water molecules. As shown in figure 3a, two coordination geometries of silver ions are observed in compound 3. Ag1 and Ag4 are trigonal centers surrounded by three carboxylic oxygen. Whereas, Ag2, Ag3, Ag5 and Ag6 exhibit distorted tetrahedrons with different environments. In fact, Ag2 and Ag3 are linked by four carboxylic oxygen atoms from four (L3)5- ligands, Ag5 is around two carboxylic and phosphinic oxygen from four (L3)5-, while Ag6 is cycled by two carboxylic and phosphinic oxygen of two (L3)5- anions. The bond lengths of Ag−O are in the scope of 2.201(5)2.561(5) Å, in agreement with those in compounds 1 and 2 (Table S1). The (L3)5- ligand connects thirteen silver ions in compound 3 with complicated bridging coordination mode of (η2:η2-μ4)(η2:η1-μ3)-(η1:η2-μ3)-(η2:η2-μ4)-(η2:η2-μ4) -μ13 (Figure 3b). Due to short distance between the four carboxylate and one phosphinite units, the dihedral angle made by two benzene rings is 53.97º indicated that the (L3)5- ligand is extremely distorted. Hence, the ligand looks like as a slightly opened shell surrounded by silver ions. With this mode, (L3)5- unite silver ions to develop a 3D metal-organic framework (Figure 3c). The open-framework contains narrow channels with an opening of 0.26  0.32 nm2 (measured from van der Waals surfaces) along the c-axis. In addition, lattice water molecules inhabit the channels. After getting rid of all the guest water molecules from the channels, the total accessible volume calculated by PLATON is 11.3% per unit cell. The most intriguing characteristic of the structure is the existence of a 3D inorganic skeleton in 3, which is a very important part to bolster the framework. The 3D inorganic skeleton (Figure 3d) is generated from silver phosphinite chain (Figure 3e) joined by Ag−Ag interactions (Ag1−Ag1 2.968(3) Å and Ag4−Ag4 2.9731(17) Å), which has never been reported in Ag compounds up to now.52, 55-59 Moreover, the Ag−Ag interactions between neighboring chains are strengthened by isophthalate groups of (L3)5- ligands.

Luminescent properties. Normally, Ag(I) coordination compounds have garnered significant note for the produce of luminescent materials. Thereby, we investigated the solidluminescence of 1-3 and free ligands at room temperature. Ligands of H3L1, H5L2, and H5L3 display photoluminescent emission at 329, 366 and 339 nm under 295, 353 and 313 nm radiation, respectively. These peaks probably originate from π*→n transition which leads to the weak emission. 60 Thus, there is very little contribution by carboxylate ligands to the fluorescent emission of their coordination compounds. As presented in Figure 4, the maximum intense emissions arise at 480 nm for 1, 491 nm for 2, and 499 nm for 3, respectively. Comparing to the free ligands, the emission energies of 1-3 are lower radiation, which eliminate an intra-ligand IL aroused for the three compounds.61 Given the oxidizing nature of the Ag(I), an appropriate assignment for the emissions involve excited states originated from ligand-to-metal charge transfer (LMCT) admixed with d-s/d-p transitions. 62 In addition, the emission bands of 1−3 are bathochromic-shifted by more than 120 nm compared to the luminescence spectra of the free ligands, which may come from the shorter Ag−Ag distances. Because metal-metal interactions have a strong influence on luminescence of d10 systems, the existence of Ag−Ag actions expectedly play a role in the emission of solid state. 63, 64 Based on the structures of the three compounds, the emission bands of 1−3 shift to lower energy with Ag−Ag interaction strengthen, attributed to energy level decreases in the d-s triplet-cluster-centered transitive state.48

Figure 4. The solid-state luminescence of the free ligands and 1-3.

Figure 3. (a) Repeating unit of 3; (b) Bridging mode of (L3)5-; (c) 3D framework; (d) A 1D inorganic chain along the c-axis; (e) 3D inorganic skeleton (blue stick: Ag−Ag interaction). For clarity, hydrogen atoms and lattice water molecules are neglected. Symmetry code: a: -x+1/2, y-1/2, -z+1/2; b: -x, -y, -z; c: -x+1/2, y+1/2, -z; d: -x, y, -z+1/2; e: -x+1/2, -y+1/2, -z+1; f: x, -y, z+1/2; g: x, -y, z-1/2.

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PXRD and thermogravimetric analyses. For checking the purity of 1-3 at room temperature, we surveyed the assynthesized samples with powder X-ray diffraction. The peak signatures of the experimental model are consistent with the simulation model based on the single-crystal structures (Figure S2), which demonstrates the good purity of samples. The thermal stabilities of 1, 2 and 3 were examined in a nitrogen atmosphere with thermogravimetric analysis (TGA) in the range of 25-800 ºC. TGA plots of 1 and 2 show that a weightloss step occurs between 335ºC to 500ºC, due to the decomposition of the organic ligand. On the contrary, two obvious weight loss steps appear in the curve of 3. As shown


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in Figure 5, a slow weight lessens of 2.7% in the range of 90250 °C because of the solvent molecules escape in 3. The main skeleton framework starts to decompose with an increase in temperature from 327 °C.

Fax: +86-21-66132670 (Z.-X.W.)

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT The authors acknowledge the Natural Science Foundation of Shanghai (16ZR1411400 and 17ZR1410600).

REFERENCES

Figure 5. TGA curves for compounds 1, 2 and 3.

CONCLUSIONS To sum up, we successfully synthesized three novel Ag(I) compounds with functionalized phosphonic acids by hydrothermal method and structurally determined by X-ray diffraction analyses. 1 is a 3D network composed by inorganic silver phosphinite 1D chains. Compound 2 holds a 3D structure containing inorganic silver phosphinite 2D layer, in which three types of coordination geometries with the ten Ag atoms observed. Compound 3 exhibits an open-framework containing narrow channels with an opening of 0.26  0.32 nm2. The interesting character of 3 is the existence of a 3D inorganic network, which is the first example observed in silver compounds. The photoluminescent properties were also investigated at room temperature with the solid crystal sample of compounds 1-3. As the three compounds have various of silver phosphinate inorganic architectures from 1D to 3D, the emission bands shift to lower energy with Ag−Ag interaction increase.

ASSOCIATED CONTENT Supporting Information. X-ray crystallographic data in CIF files, selected bond lengths, IR, and PXRD for 1-3 are free obtained at http://pubs.acs.org. Accession Codes CCDC 1890788-1890790 contain the supplementary crystallographic data for this paper. These data can be available freely 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.

AUTHOR INFORMATION Corresponding Author * E-mail: zxwang@ shu.edu.cn (Z.-X.W.)

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SYNOPSIS TOC Various of Silver Phosphinate Inorganic Architectures in Three-Dimensional Frameworks with Argentophilic Interactions Meng-Qin He, Ye Xu, Ming-Xing Li, Min Shao and Zhao-Xi Wang Three novel Ag(I) compounds with functionalized phosphonic acids containing 1D, 2D or 3D silver phosphinate inorganic architectures with argentophilic interactions were synthesized and characterized. The compounds exhibit the photoluminescent emission bands shift to lower energy with Ag−Ag interaction increase.


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Various of Silver Phosphinate Inorganic Architectures in Three

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