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Synthesis, structural characterization, photophysical properties and antibacterial assessment of silver(I)- thione coordination polymers based on a competition between nitrate anion and co- anions CF3SO3-, ClO4-, BF4-, PF6- and SbF6Susan Soleymani-Babadi, Azizolla Beheshti, Maryam Bahrani-Pour, Peter Mayer, Hossein Motamedi, Damian Trzybi#ski, and Krzysztof Wozniak Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00038 • Publication Date (Web): 28 May 2019 Downloaded from pubs.acs.org on July 17, 2019

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Crystal Growth & Design

Synthesis, structural characterization, photophysical properties and antibacterial assessment of silver(I)- thione coordination polymers based on a competition between nitrate anion and co- anions CF3SO3−, ClO4−, BF4−, PF6− and SbF6−

Susan Soleymani-Babadia, Azizolla Beheshti*a, Maryam Bahrani-Poura, Peter Mayerb, Hossein Motamedic,d,Damian Trzybińskie and Krzysztof Wozniakf a

Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz,

Iran b c

LMU München Department Chemie Butenandtstr, 5-13 (D)81377 München ,Germany

Department of Biology, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz,

Iran d

Biotechnology and Biological Science Research Center, Shahid Chamran University of

Ahvaz, Ahvaz, Iran e

Biological and Chemical Research Centre, Chemistry Department, University of Warsaw,

Żwirki i Wigury 101, 02-089 Warszawa f

Chemistry Department, Warsaw Univeristy, Pasteura 1, 02-093 Warsaw, Poland

*E-mail: [email protected] Abstract Six new coordination polymers namely, [Ag2L(NO3)2]n (1), {[Ag6L4(CF3SO3)4 ][CF3SO3]2}n (2), {[Ag2L(NO3)][ClO4]}n (3), {[Ag2L(NO3)][BF4]}n (4), {[Ag2L(NO3)][PF6]}n (5) and {[Ag2L(NO3)][SbF6]}n (6) have been successfully synthesized by the reaction of AgNO3 and selected co-anions CF3SO3−, ClO4−, BF4−, PF6− and SbF6− with 1, 3- bis (1methylthioimidazolyl) propane under the same experimental condition in order to illustrate coordination ability of nitrate ion relative to the other considered co-anions. To evaluate this competition, compound 1 as a reference structure was synthesized in the absence of coanions. In its 2D structure, the thione ligand appears in a hexadentate mode and the nitrate as a co-ligand is coordinated in a bidentate fashion. In a competition between the silver nitrate and triflate, despite of coordination ability expected for both anions, these anions were not appeared together in the structure of compound. moderately coordinating anion CF3SO3− 1 ACS Paragon Plus Environment

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build up a cationic structure with only one kind of anion. In contrast to polymers 1 and 2, in the valuable networks 3-6, for the first time extraordinary two kind of anions were involved in their structures. The difference between the coordination ability of the considered coanions is the most effective factor which impact on the coordination and linkage modes of the flexible ligand and nitrate anion and in turn directing the construction of coordination polymers. In general, X-ray diffraction analysis reveals that the most changes in the structure of compounds 3-6 relative to the structure of 1 were generated by the bulky, uncoordinated anions PF6− and SbF6−. The TGA experimental data reveal that these compounds start to decompose in the temperature range of 140-328˚C. In their electronic spectra, sharp band at 246 nm due to the π → π* transitions in the C=S moiety of the ligand is slightly red-shifted upon coordination of the ligand to AgI ions via sulphur atoms. All of the synthesized compounds display a strong blue emissions in the solid state. The title complexes possess antibacterial activity against the selected strain of Gram-negative (Escherichia coli, Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus, Bacillus subtilis) bacteria.

Introduction In recent decades, the construction of metal–organic network architectures has continued to attract great attention due to not only the intriguing variety of their structures and new topologies, but also to their potential exploitable properties.1-15 The properties of materials composed of coordination polymers depend on their network topology. Thus, it is pertinent to understand and control the subtle factors that have some impact on the formation of these materials. The self-assembly progress is highly influenced by several factors such as the ligand and metal nature,16-23 the counter ions,24-30 the experimental conditions,31-34 the solvents,

35-39

and the metal to ligand ratio.40-41 It is noteworthy to

mention that, in metal-organic crystal engineering, predicting the coordination polymer topology when mixed anions are used is more difficult because several factors are controlling the framework formation of coordination polymers including the size, geometry ,coordinating ability and selectivity of anions to participate in the structure.42-46 On the other hand, the role of the anions in the macromolecule chemistry is of a great interest because of its application in ion - pair recognition and especially in anion exchange.47-52 Although a good number of metal mixed-ligand complexes were reported,53-56 but to the best of our knowledge there is no any report in the literature

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about

the synthesis of metal mixed-anion complexes. Mixed anion complexes are

attractive due to their potential applications and their new structures. In recent years, many researchers have undertaken considerable work on the synthesis of new silver(I) coordination polymers with flexible dithioether ligands.57-62 However the coordination chemistry of the flexible organochalcogenone ligands 1,n- bis( 3-methylimidazole-2thione) alkane has not been studied in detail in spite of their potential applications in the biomedical science as well as their interesting structural coordination chemistry. 63-75 The sulphur atom in dithione ligands has two lone pair electrons which can take part in coordination to metal ions. The S donors of dithione ligands coordinated to silver ion with monodentate, µ2-S and µ3-S bridging or chelating, combining bridging coordination modes and expand the coordination sphere of the metal centers into extended solid state networks .76-78 On the other hand, the silver(I) ion is a soft Lewis acid and hence has a good ability to coordinate to sulphur atom of a dithione that is a soft Lewis base.79 Beside that, the silver(I) ion (d10) has a flexible coordination sphere, ranging from 2 to 6 and high ability for metal···metal interactions.80 To have a better understanding of the impact of anions and especially their competition in directing the final structure and topology of the title polymers, we have synthesized and structurally characterized six new coordination polymers with structural diversity by the reaction of AgNO3 and 1, 3bis (1-methylthioimidazolyl) propane (chart 1) with co- anions CF3SO3−, ClO4−, BF4−, PF6− and SbF6− under the same reaction conditions. In addition, the antibacterial assessment, photo physical properties and thermal analysis of these complexes were also studied.

S H3C

S CH3

N

N

N *

N

Chart 1

Experimental section Materials and general methods



All experiments were carried out in air atmosphere. Starting materials were reagent grade and used as commercially obtained without further purification. The 1, 3- bis(1methylthioimidazolyl) propane as a ligand was prepared by the literature methods 69,81-83 with relatively high yield (76%) via the reaction of 1-methylimidazole with the 1,3-dibromoproane and S8 in the presence of K2CO3. Infrared spectra (4000 - 400 cm-1) were recorded from KBr disks with a BOMEN MB102 FT-IR spectrometer. Elemental analyses for C, H and N were implemented on a Thermo Finigan Flash EA 1120 CHN analyzer. Thermal analyses were performed using a SDT Q600 V20.9 Build 20 thermal analyzer. A ramp rate of 10 °C.min-1in the range of 20-900°C was used. UV–Vis spectra were measured with a Photonix Ar 2015, I.R.spectrophotometer. Fluorescence spectra of the solid samples were recorded on a Hitachi F-7000 fluorescence spectrophotometer. X-ray powder diffraction patterns were recorded on a Philips X’Pert Pro diffractometer (Cu Kα radiation, λ = 1.54184 Å) in the 2θ range 5-50°. CAUTION: Perchlorate compounds are potentially explosive and should be handled with care. Syntheses of complexes Colorless single crystals suitable for X-ray diffraction analysis for complexes were obtained by the method branched tube. The ligand (0.1 mmol), silver(I) nitrate (0.2 mmol) and a selective salt of a co-anion (0.4 mmol) were placed in the main arm of a branched tube and methanol-water mixture (3:1 v/v) was added to fill the arms. The tube was sealed and the arm containing the reagents was immersed in an oil bath at 60 °C while the other arm was kept at ambient temperature. After 1-4 days, the colorless needle-like or prism-shaped crystals of the complexes suitable for X-ray diffraction analysis were deposited in the cooler arm. [Ag2L(NO3)2]n (1) Compound 1 was synthesized with a good yield (80%) without using a co-anion. Anal. calcd. (%) for Ag2C11H16N6O6S2: C, 21.72; H, 2.65; N, 13.82. Found: C, 21.05; H, 2.44; N, 13.29. IR (KBr pellet, cm-1): 3150m, 3120m, 2944w, 1626w, 1569s, 1488s, 1430vs- 1185s, 1293vs, 1248m, 1233m, 1165m, 1094w, 1066w, 1034m, 815m, 759s, 686m, 622w, 616w, 507m, 483w. {[Ag6L4(CF3SO3)4 ] [CF3SO3]2}n (2)


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The co-anion salt involved in this reaction was AgCF3SO3 (yield: 75%). Anal. calcd. (%) for Ag4C50H64F18N16O18S14: C, 25.03; H, 2.69; N, 9.34. Found: C, 25.55; H, 2.36; N, 9.89. IR (KBr pellet, cm-1): 3136m, 2951w, 1574m, 1491m, 1422m, 1306-1213vs, 1167vs, 1097w, 1030vs, 742m, 682m, 638vs, 576m, 519s. {[Ag2L (NO3)][ClO4]}n (3) The appropriate co-anion salt participated in this reaction was NaClO4.H2O (yield: 51%). Anal. calcd. (%) for Ag2 C11H16N5O7S2Cl: C, 20.46; H, 2.50; N, 10.85. Found: C, 21.07; H, 2.81; N, 10.44. IR (KBr pellet, cm-1): 3166m, 3140m, 2931w, 1567m, 1485m, 1385vs, 1246m, 1196w, 1057-1140vs, 752s, 686m, 626s, 512w, 483w. {[Ag2L (NO3)][BF4]}n (4) The suitable co-anion salt used in this reaction was NaBF4 (yield: 53%). Anal. calcd. (%) for Ag2C11H16N5O3S2BF4: C, 20.87; H, 2.55; N, 11.06. Found: C, 20.39; H, 2.21; N, 10.72. IR (KBr pellet, cm-1): 3169w, 3146m, 2934w, 1571s, 1485s, 1419s, 1385vs, 1289s, 1246m, 1193w, 1004vs- 1140vs, 868w, 749s, 682m, 666w, 520m, 483w. {[Ag2L (NO3)][PF6]}n (5) The selected co-anion salt counterpart in this reaction was KPF6 (yield: 43%). Anal. calcd. (%) for Ag2C11H16N5O3S2PF6: C, 19.12; H, 2.33; N, 10.13. Found: C, 19.65; H, 2.66; N, 10.61. IR (KBr pellet, cm-1 ): 3179m, 3156w, 2947w, 1574s, 1488m, 1452m, 1428m, 1385s, 1312s, 1246m, 1193m, 1167m, 1094m, 1060w, 1037w, 842vs, 749s, 682m, 563s, 509w, 481w. [Ag2L (NO3)][SbF6]}n (6) The co-anion salt involved in this reaction was KSbF6 (yield: 44%). Anal. calcd. (%) for Ag2C11H16N5O3S2SbF6: C, 16.90; H, 2.06; N, 8.96. Found: C, 17.45; H, 2.36; N, 8.49. IR (KBr pellet, cm-1 ): 3179m, 3156w, 2947w, 1574s, 1488m, 1452m, 1428m, 1385s, 1302vs, 1246m, 1193m, 1167m, 1094m, 1060w, 1037w, 749vs, 682s, 663vs, 509w, 481w. X-ray crystallography Good quality single-crystals of 1−6 were selected for X-ray diffraction data collection. Diffraction data were collected at 105 (2) K (for polymer 1), 106 (2) K (for polymer 2), 293 (2) K (for polymers 3 and 6), 100 (2) K (for polymers 4 and 5) on a Bruker D8 Venture 5 ACS Paragon Plus Environment


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diffractometer using graphite mono chromated MoKa ( = 0.71073 Å) ( for 1−3 and 5-6) and Rigaku Oxford Diffraction SuperNova Dual Source diffractometer with CuKa ( = 1.54184 Å) using CrysAlis RED software ( for polymer 4).84 The multi-scan empirical absorption correction using spherical harmonics ( for 1−3 and 5-6) and numerical absorption correction based on gaussian integration over a multifaceted crystal model ( for 4) implemented in SCALE3 ABSPACK scaling algorithm were applied.86 In the case of 1−3 and 5-6 the structures were solved by direct method with SIR97

85

and refined with full-matrix least-

squares techniques on F2 with SHELXL-97.86 For compound 4, the structural determination procedure was carried out using the SHELX package.87 The structure of 4 was solved with direct methods and then successive least-square refinement was carried out based on the fullmatrix least-squares method on F2 using the XLMP program.87 All H-atoms were positioned geometrically with C–H equal to 0.93, 0.96 and 0.97 Å for the aromatic, methyl and methylene H-atoms, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.2 for the aromatic and methylene H-atoms, and x = 1.5 for the methyl H-atoms. The molecular structure plots were prepared using Mercury.87 Antibacterial activity assessments In order to find the possible antibacterial potential of the synthesized compounds, the standard Kirby-Bauer disc diffusion method was followed according to CLSI (Clinical and Laboratory Standards Institute) guidelines.89 Briefly, different concentrations of each complex including 5, 10, 20 and 40 mg/ml were prepared in DMSO and sterile blank disks (6.4 mm diameter) were submerged in these solutions. So saturated discs were prepared with 0.2, 0.4, 0.8 and 1.6 mg effective dose per disc. As a target organism Staphylococcus aureus (ATCC 6538) and Bacillus subtilis (ATCC 6633) as Gram positive bacterial species and Escherichia coli (ATCC 25922) and Pseudomonas aeruginosa (ATCC 9027) as Gram negative bacterial species were selected and following bacterial growth in Mueller-Hinton broth (Merck, Germany) till 0.5McFarland turbidity, a lawn culture was prepared MullerHinton agar (Merck, Germany). The prepared discs were placed on lawn culture and plates were incubated at 37°C for 24h. The inhibition zone diameter around each disc was measured and recorded (mm). MIC and MBC indices


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The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) indices were investigated to evaluate the minimum effective concentration for inhibition of bacterial growth and killing bacterial cell, respectively. Serial two fold dilutions from 64 to 0.5 mg/ml of each complex was prepared in 1 mL sterile Mueller- Hinton broth and the tubes were inoculated with 100 µl of 0.5 McFarland suspension of bacterial culture. Following incubation at37°C for 24h the turbidity of tubes were assessed. Those tubes that remained clear was regarded as growth negative and the least concentration that inhibited bacterial growth was regarded as MIC. A streak culture was prepared from culture negative tubes on Mueller- Hinton Agar and following incubation the least concentration that inhibited colony formation was reported as MBS.


Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46

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Table 1. Crystallographic data and structure refinement parameters for polymers 1-6. 1 net formula Mr/g mol−1 crystal size/mm T/K radiation diffractometer

C11H16Ag2N6O6S2 608.16 0.100 × 0.010 × 0.010 105.(2) MoKα Bruker D8 Venture TXS

crystal system orthorhombic space group Fdd2 a/Å 20.454(3) b/Å 40.652(7) c/Å 4.2576(6) α/° 90 β/° 90 γ/° 90 3 V/Å 3540.2(9) Z 8 −3 calc. density/g cm 2.282 −1 μ/mm 2.493 absorption correction Multi-Scan transmission factor range 0.6200–0.7454 refls. measured 3972 Rint 0.0439 mean σ(I)/I 0.0571 θ range 3.607–26.344 observed refls. 1467 x, y (weighting scheme) 0, 10.9684 hydrogen refinement constr refls in refinement 1583 parameters 124 restraints 1 R(Fobs) 0.0357 2 Rw(F ) 0.0704 S 1.113 shift/errormax 0.001 max electron density/e Å−3 0.712 min electron density/e Å−3 −0.734

2

3

4

5

6

C50H64Ag6F18N16O18S14 2615.23 0.090 × 0.010 × 0.010 106.(2) MoKα Bruker D8 Venture TXS

C11H16Ag2ClN5O7S2 645.60 0.040 × 0.010 × 0.010 293.(2) MoKα Bruker D8 Venture TXS

C11H16Ag2F6N5O3PS2 691.12 0.080 × 0.020 × 0.010 100.(2) MoKα Bruker D8 Venture TXS

C11H16Ag2F6N5O3S2Sb 781.90 0.050 × 0.010 × 0.010 293.(2) MoKα Bruker D8 Venture TXS

triclinic P -1 16.0513(11) 16.3196(10) 16.5696(10) 99.730(2) 100.848(2) 93.947(2) 4178.8(5) 2 2.078 1.840 Multi-Scan 0.6680–0.7454 56053 0.0797 0.0831 3.170–26.373 12409 0.0001, 29.6451 constr 17020 1092 19 0.0594 0.1184 1.035 0.001 1.426 −1.628

orthorhombic Pnma 27.9053(14) 14.1863(6) 4.7151(2) 90 90 90 1866.58(15) 4 2.297 2.512 Multi-Scan 0.5891–0.7454 14038 0.0464 0.0280 3.254–26.356 1564 0.0280, 11.6876 constr 1971 137 3 0.0444 0.0991 1.053 0.001 1.263 −0.910

C11H16Ag2BN5O3F4S2 632.96 0.13 x 0.08 x 0.03 100(2) CuKα Rigaku OD SuperNova Dual Source orthorhombic Pnma 27.5909(17) 14.0080(9) 4.6440(3) 90 90 90 1794.88(19) 8 2.342 20.313 Gaussian 0.271−0.636 4971 0.0407 0.0444 3.20−67.06 1683 0.0452, 1.8069 constr 1683 137 0 0.0487 0.0843 1.090 0.002 1.608 -0.645




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Table 2. Selected bond distances(Å) and bond angles (˚) for compounds 1- 6. Compound

bond distances

(Å)

bond angles

1

Ag(1)-S(1) Ag(1)-S(1) Ag(1)-S(1) Ag(1)-O(1) Ag(1)-O(2)

2.506 2.653 2.756 2.321 2.623

O(1)-Ag(1)-O(2) S(1)-Ag(1)-S(1) S(1)-Ag(1)-O(1) S(1)-Ag(1)-S(1) S(1)-Ag(1)-O(2) S(1)-Ag(1)-O(1) S(1)-Ag(1)-O(2) S(1)-Ag(1)-O(2) S(1)-Ag(1)-O(1)

51.37 88.43 107.95 88.43 105.21 89.89 120.14 131.04 132.72

2

Ag(1)-S(1) Ag(1)-S(7) Ag(1)-S(8) Ag(1)-O(1) Ag(2)-S(1) Ag(2)-S(2) Ag(2)-S(4) Ag(2)-O(6) Ag(3)-S(2) Ag(3)-S(3) Ag(3)-O(4) Ag(4)-S(3) Ag(4)-S(4) Ag(4)-S(5) Ag(4)-O(7) Ag(5)-S(5) Ag(5)-S(7) Ag(5)-S(6) Ag(6)-S(6) Ag(6)-S(7) Ag(6)-S(8) Ag(6)-O(13)

2.516 2.552 2.556 2.447 2.491 2.574 2.552 2.577 2.486 2.489 2.489 2.472 2.467 2.700 2.390 2.459 2.473 2.794 2.451 2.889 2.406 2.411

S(1)-Ag(1)-S(7) S(1)-Ag(1)-S(8) S(7)-Ag(1)-S(8) S(8)-Ag(1)-O(1) S(1)-Ag(2)-S(2) S(2)-Ag(2)-S(4) S(1)-Ag(2)-S(4) S(1)-Ag(2)-O(6) S(3)-Ag(3)-S(2) S(2)-Ag(3)-O(4) S(3)-Ag(3)-O(4) S(3)-Ag(4)-S(4) S(3)-Ag(4)-S(5) S(4)-Ag(4)-S(5) S(3)-Ag(4)-O(7) S(5)-Ag(5)-S(7) S(5)-Ag(5)-S(6) S(6)-Ag(5)-S(7) S(6)-Ag(6)-S(7) S(6)-Ag(6)-S(8) S(7)-Ag(6)-S(8) S(8)-Ag(6)-O(13)

112.81 101.43 119.91 106.31 128.92 97.59 122.59 94.46 148.94 99.04 88.52 144.97 100.72 94.77 107.26 105.61 123.90 84.71 83.10 256.27 112.46 108.18

3


2.540 2.689 2.731 2. 587 2. 588

S(1)-Ag(1)-S(1) S(1)-Ag(1)-S(1) S(1)-Ag(1)-S(1) O(1)-Ag(1)-O(2) S(1)-Ag(1)-O(1) S(1)-Ag(1)-O(2) S(1)-Ag(1)-O(2)

105.41 111.04 126.88 77.43 149.29 117.36 87.44

4


2.540 2.670 2.707 2. 559 2. 597

S(1)-Ag(1)-S(1) S(1)-Ag(1)-S(1) S(1)-Ag(1)-S(1) O(1)-Ag(1)-O(2) S(1)-Ag(1)-O(1) S(1)-Ag(1)-O(2) S(1)-Ag(1)-O(1) S(2)-Ag(2)-O(4)

113.21 108.00 124.48 49.41 86.29 72.25 91.04 114.68

5

Ag(1)-S(1) Ag(1)-S(2) Ag(1)-O(2) Ag(2)-O(1) Ag(2)-O(3) Ag(2)-S(1) Ag(2)-S(2)

2.499 2.474 2.620 2.501 2.692 2.474 2.490

S(1)-Ag(1)-S(2) S(1)-Ag(1)-O(2) S(2)-Ag(1)-O(2) O(1)-Ag(2)-O(3) S(2)-Ag(2)-S(1) S(1)-Ag(2)-O(1) O(1)-Ag(2)-S(2)

166.49 80.95 112.08 77.43 149.29 117.36 87.44

6

Ag(1)-S(1) Ag(1)-S(2) Ag(1)-O(2) Ag(1)-O(3) Ag(2)-S(1) Ag(2)-S(2) Ag(2)-O(1)

2.479 2.502 2.699 2.716 2.495 2.479 2.518

S(1)-Ag(1)-S(2) S(1)-Ag(1)-O(2) S(1)-Ag(1)-O(3) S(2)-Ag(1)-O(2) S(2)-Ag(1)-O(3) O(2)-Ag(1)-O(3) S(1)-Ag(2)-O(1) S(1)-Ag(2)-S(2) S(2)-Ag(2)-O(1)

166.75 108.24 104.03 83.51 88.51 45.80 87.05 149.54 118.75


(˚)


Results and discussion Description of crystal structures [Ag2L(NO3)2]n (1) The coordination polymer of 1 crystallizes in Fdd2 orthorhombic space group with Z=8 (Table 1). To the best of our knowledge, 1 is the first documented metal-organic complex of the 1,3-bis(1-methylthioimidazolyl) propane ligand. In this structure, each ditopic ligand is connected to six different metal centers via bis(µ3-S) mode and each silver atom is linked to three sulfur atoms belonging to three distinct ligands (Figure 1a). In doing so, zigzag ladders of rectangular Ag2S2 extending along the c-axis are obtained. In turn, adjacent zigzag ladders were connected to each other by the organic spacer ligands to create a 2D-network structure (Figure 1b). The coordination sphere of metal center is completed by two oxygen atoms of a nitrate anion with a bidentate coordination mode (Ag–O distances of 2.623 and 2.321 Å). The average Ag–S bond length of 2.638 Å is best described as a distorted trigonal bipyramid around the silver atom.72 The values for the bond angles around the central atom are in the range of 51.37° (O1- Ag1-O2) to 132.72°(S1-Ag1-O1) (Table 2). The Ag···Ag separation in the distorted rectangular Ag2S2 rings is 3.86 Å which is slightly longer than the sum of the van der Waals radii of silver atoms (3.44 Å). Therefore, there are no signifiant silver-silver interactions in the basic Ag2S2 units. In this structure, the flexible ligand adopts anti-anti conformation with S···S separation of 7.740 Å. This complex forms a non-interpenetrating framework and the nitrate groups are located inside of the layers with an anti-conformation (Figure 1c). The layer structures of 1 are further stabilized through the hydrogen bonds between the oxygen atoms that are not engaged with the AgI centers and the hydrogen atoms of the methyl imidazole rings of neighboring neutral sheets with a minimum distance of 2.326 Å to generate a network structure with an ABAB… sequence (Figure 1c).


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Figure 1. (a) Perspective view of coordination environment of Ag I in polymer 1. Atomic displacement parameters are drawn at 35% probability level. (b) The 2D coordination polymer of 1 extending parallel to the ac plane. Nitrate anions were omitted for clarity. (c) Packing of the 2D- strcture of 1 along the b-axis. Hydrogen atoms were omitted for clarity in figures 1a and 1b.

{[Ag6L4(CF3SO3)4 ][CF3SO3]2}n (2) Coordination polymer of 2 crystallizes in the triclinic space group P-1 with Z= 2 (Table 1). In the asymmetric unit of 2, six different AgI centers with three kinds of coordination geometry are linked together by four L ligands with three coordination fashions to form three rings with 4, 5 and 8 membered of Ag and S atoms (Figure 2a). In this structure, ligand is connected to metal centers via respective coordination modes: Chelating combining µ2 and µ3-bridging, chelating combining bis µ2-bridging and bis µ2-bridging with the anti-gauche conformation. Ag(1) center adopts a distorted tetrahedral geometry coordinated by three S atoms from two independent ligands (2µ2-S and µ3-S) and one oxygen atom from a terminal triflate with valence angles ranging from 88.23 to 129.63°. The second metal center [Ag(2) ]is also fourcoordinated by three S atoms from two distinct ligands (3µ2-S) and an oxygen atom from one triflate ligands with µ-O,O′ coordination mode. In turn, the other oxygen of the considered anion is connected to Ag(2) and Ag(3) ions. The coordination sphere of Ag(3) is completed by two sulfur atoms(µ2-S ) from two distinct ligand and one adjacent silver atom (Ag4 ) which is weakly bonded with silver···silver distance of 3.04 Å. By ignoring the silver–silver interactions, the sum of the angles around the Ag(3) (336.50°) demonstrated a distorted 11 ACS Paragon Plus Environment


trigonal pyramidal for this metal center. An uncoordinated trifate anion neutralizes the remaining positive charge associated with silvers (2) and (3). The Ag(4) center has a distorted tetrahedral environment, which is coordinated to three sulfur atoms from three distinct ligands (µ2-S) and one oxygen atom from a terminal triflate. The Ag(5) is surrounded by three S atoms(2µ2-S and µ3-S) from two independent ligands in a distorted pyramidal planar arrangement (359.22°). The values for the bond angles around the Ag(5) center are in the range of 84.71to 150.61°. The positive electrical charge of the Ag (5) is neutralized by a counter anion. Ag(6) is four-coordinated by three S atoms of two ligands with a chelating combining coordination mode and an oxygen atom from one triflate anion. The Ag–S bond lengths of 2 (2.700- 2.451 Å) are in the normal range for the Ag-S bond distances.72 In this polymer, two thirds of triflate anions are coordinated to the Ag centers and the rest remained uncoordinated. The Ag-O distances are 2.447, 2.577, 2.489, 2.390 Å for the Ag(1) to Ag(4), respectively and 2.611 Å for the Ag(6). These values are in the normal range for an Ag–O bond length (Table 2).89,90 The whole disordered chain structure with variable coordination modes for the silver centers can be described as two infinite single lines of [-Ag-µ2-(S)-Ag-]n bonded together by the µ2-S of unchelated ligand and µ3-S donor atoms (Figure 2b). Each of the chains is surrounded by six neighboring crystallographic similar chains in a hexagonal arrangement where the very weak intermolecular hydrogen bonds were detected between the CF3SO3− anions and hydrogen atoms of the side methyl groups of the ligand (Figure 2c).

Figure 2. (a) Partial view of the asymmetric unit of the coordination polymer 2 and coordination modes of ligand and anions (Each of the coordination modes of ligand and anions was shown separately with a different


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color.). (b) The 1D coordination polymer of 2 (without shown counter ions). (c) Packing of the 1D strcture of 2. Hydrogen atoms were omitted for clarity.

{[Ag2L(NO3)][ClO4]}n (3) The self-assembly of ligand, silver nitrate and sodium perchlorate, give rise to a twodimensional ionic network of 3. It is crystallizes in the Pnma orthorhombic space group with Z= 4 (Table 1). In this structure, uncommonly the nitrate and perchlorate act as coordinated and uncoordinated to the AgI center, respectively. In its cationic network, one crystallographic independent AgI center adopts a distorted trigonal bipyramidal environment. The metal center is coordinated to two oxygen atoms from one nitrate anion (Ag–O distances of 2.587 and 2.588 Å) and to three sulfur atoms from three distinct ligands (average Ag–S bond length of 2.653 Å) (Figure 3a). The coordination sphere is completed by two adjacent silver atoms which are weakly bonded with silver–silver distances of 3.120 Å. Silver centers are linked to one another by the L ligand as a building block via a µ3-S bridge to build up a coordination network of [Ag2L]2+n parallel to the bc-plane (Figure 3b). On the basis of the considered coordination mode of AgI center, zigzag ladders of rectangular Ag2S2 extending along the c-axis were obtained. The [Ag2L]2+n cationic sheets were further stabilized through the nitrate anions bridging between the neighboring ladders to generate a network structure of [Ag2L(NO3)]+n (Figure 3c) where the perchlorate anions are sandwiched between the sheets (Figure 3d). The crystal structure of 3 revealed the presence of a rare coordination mode of Ƞ3-µ2-NO3− ligand bridging chelate two AgI centers to provide the first example of this coordination mode for NO3−. Each of the tridentate bridging chelate nitrate ions is connected to two metal centers with unprecedented coordination mode, so that one of the oxygen donor atoms bridges two AgI centers and at the same time the other two are bonded to the same silver atoms. The intermolecular hydrogen bond interactions were detected between the oxygen atoms of the perchlorate ion and the hydrogen atoms of the hydrogen atoms of the methyl imidazole ring of the ligand.



Figure 3. (a) Atomic numbering and coordination environment of AgI in polymer 3 (Ellipsoid probability 35%). (b) The cationic sheet of [Ag2L]2+n parallel to the bc-plane showing the 4-membered Ag2S2 and 20 membered Ag2L2 metallo-macrocycles. (c) network structure of [Ag2L (NO3)]+n (d) View of the packing of 3 showing sheets with an AAA… array while anions are located between the cationic sheets. Hydrogen atoms were omitted for clarity. Hydrogen atoms were omitted for clarity.

{[Ag2L(NO3)][BF4]}n (4) In view to obtain detailed information of the impact of competition between counter anions on the structure of the complexes, in the preparation of 4, NaBF4 was used instead of NaClO4. Similar to the polymer 3, ionic polymer 4 is made up by Ag2S2 ladders that are connected to each other by organic linker ligands and nitrate anions to form a cationic 2D structure of [Ag2LNO3]+n parallel to the ac –plan (Figure 4b), where the uncoordinated tetrafluoroborate anions are located between the layers to balance the charge of the polymer(Figure 4c). Like the structure of 3, the metal–metal interactions in the base units Ag2S2 of the ladders are extending in c axis to form a zigzag molecular wire with an Ag···Ag distance of 3.013 Å. As depicted in Figure 4a, the AgI ion involved in a distorted trigonal bipyramidal coordination geometry comprising of three S donor atoms (average Ag–S bond length of 2.639 Å) from three distinct ligands with S–Ag–S bond angles ranging from 49.41 to 124.48° and two O atom from one nitrate (Ag–O = 2.559 and 2.597 Å). Intermolecular hydrogen bond interactions were observed between the fluorine of the BF4− anion and hydrogen atoms of the ligand with minimum distance of 2.553 Å.


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Figure 4. (a) Distorted trigonal bipyramidal environment of AgI in polymer 4. (b) The cationic sheets of {[Ag2L(NO3)]+}n parallel to the ac-plane. (c) View of the packing of 4. Hydrogen atoms were omitted for clarity.

{[Ag2L (NO3)][PF6]}n (5) Reaction of L ligand with AgNO3 and KPF6 give rise to complex 5 which consisting of an extended cation chain of [Ag2L(NO3)]+ and PF6− anions. In each of the chains, there are two crystallographic independent silver atoms with two kinds of coordination geometry (Figure 5b). Ag)2) adopts a pseudo-tetrahedral geometry coordinated by two sulfur atoms(Ag–S = 2.490 and 2.474 Å ) from two distinct ligands and two oxygen atoms (Ag–O =2.501 and 2.691Å ) of two nitrate anions, while the second one [Ag(1) ] has a nearly linear coordination geometry of sulfur atoms(Ag–S =2.474 and 2.499 Å ) of one ligand with an S-Ag(2)-S angle of 166.49°. The third ligand is an oxygen atom (Ag–O =2.620 Å) from the nitrate anion showing a slightly distorted T-shape coordination geometry around the AgI center with a deviation from the ideal coordination plane by ca. 0.48Å (Table 2). In this structure, each of the L ligands is connected to Ag(1) centers with chelating combining bis µ2-bridging coordination mode to form the first core structure. Both of these cores were subsequently joined together by two Ag(2) center to create a subunit (Figure 5a). The subunits are in turn connected by two nitrate anions (Figure 5b) to build up a chain propagated along the a-axis (Figure 5c). In the tetranuclear subunit of 5, each of the S atoms of ligands adopts a µ2-S bridging mode to connect two silver atoms. Thus, four silver centers are linked by four sulfur 15 ACS Paragon Plus Environment


atoms from two independent chelating ligands to form an eight-membered Ag4S4 ring, which adopts a chair conformation. In the eight -membered ring, the four AgI centers are approximately planar and form a rectangle with side lengths (the adjacent Ag···Ag distances) of 3.252 and 3.132 Å, and diagonal lengths of 4.540 and 4.492 Å, respectively. The silversilver distance in side lengths of subunit is less than the sum of the van der Waals radii of two silver atoms and is consistent with a weak metal···metal interaction. In this cationic structure, each oxygen atom of one nitrate is connected to one silver ion with a rare coordination mode of the nitrate ion (Ƞ3-µ3-NO3−). In the other word, the nitrate group was coordinated to three metal center of the two adjacent subunits. Structural analysis between the polymers 1-5 reveals that in the 1D structure of polymer 5, the nitrate ion as a co-ligand has a critical role in directing the structure of this compound. The PF6− anions counterbalance the charge of the cationic chains. Each of the chains is surrounded by the other four neighboring ones. They are bound to one another via P–F…H–C interactions with F···H bond length of 2.75 Å. A 3D network may be considered when these interactions are taken into account (Figure 5d).

Figure 5. (a) The tetranuclear subunit of 5 (b) Connection of cationic subunits through the nitrate anions with tridentate coordination mode in compounds 5. (c) One-dimensional coordination polymer of 5 parallel to the aaxis. (d) Projection down the a-axis, showing the packing of double-stranded of the 1D coordination polymer. Hydrogen atoms were omitted for clarity.

{[Ag2L (NO3)][SbF6]}n (6)


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The self-assembly of 1,3-bis(1-methylthioimidazolyl) propane and silver nitrate with a salt bearing SbF6− anion give rise to a cationic 1D-coordination network of 6. Since PF6− and SbF6− have octahedral geometry, we have synthesized coordination polymer 6 with the SbF6− expecting that its topology would be identical to that obtained for the PF6−, 5. Compound 6 has a similar cationic chain structure and packing mode to that of 5. However, in contrast to the structure of 5, nitrate anion shows a different coordination mode(Ƞ3-µ2-NO3−). As depicted in Figure 6a, one nitrate anion acts as a bridge between two silver centers of the adjacent subunits with mono and bi-dentate mode. In this structure, the Ag(1) ion involved in a pseudo-tetrahedral coordination geometry comprising of two S donor atoms(Ag-S=2.502 and 2.479 Å ) from one ligands and two O atoms (Ag-O=2.716 and 2.699 Å )from one nitrate ion with bond angles ranging from 45.00 to 166.75°. The Ag(2) is surrounded by three atoms: two sulfur atoms from two independent ligands with average Ag-S distance of 2.487 Å and one oxygen of a nitrate anion with an Ag-O length of 2.518 Å. The sum of the angles around the Ag(2) atom (354.34°) demonstrate a trigonal pyramidal or T-shaped geometry for the central atom. As in the structure of 5, in 6 the coordination modes of ligand and metal center result in a tubular supramolecular architecture that propagates along the a-axis while the nitrate anions are located inside the tunnel (Figure 6b). Each of these cationic tubular chains is surrounded by four others via Sb–F···H–C interactions with F···H distance of 2.635Å and adopts a tetragonal mode of packing (Figure 6c). The hexafluoroantimonate )SbF6−( anions lie between the neighboring cationic tubes and counterbalance their charges.



Figure 6. (a) Connection of cationic subunits through the nitrate anions with a tridentate chelating coordination mode (Ƞ3-µ2-NO3−) in compound 6. (b) One-dimensional coordination polymer of 5 parallel to the a-axis (the skeleton of ligand was omitted). (c) Projection down the a-axis showing the packing of the double-stranded 1D coordination polymer. Hydrogen atoms were omitted for clarity.

Synthesis and general characterizations The silver(I)- based polymers 1-6 with a good yield were synthesized in air atmosphere via one–pot reactions in methanol/water (3/1) as a solvent by an AgI-ligand and a co- anion with a ratio of 2:1;4. However, these polymers can also be obtained by the reaction of compound 1 with the selected co-anions CF3SO3−, ClO4−, BF4−, PF6− and SbF6−. In the syntheses of polymers 3-6, Na+ and K+ ions only act as counter ions for the co- anions which have been used in the perpetration of these polymers. Therefore, they have not any other role in the synthesis and final morphology of the mentioned compounds. Infrared spectroscopy and elemental analyses confirmed that these compounds are stable in air and atmospheric moisture but slightly sensitive to light and are sparingly soluble in polar solvents such as DMF and CHCl3. In view to conﬁrm the phase purity of the synthesized polymers, X-ray powder diffraction experiments were carried out for compounds 1- 6 in which the results of the simulations were consistent with the experimentally observed spectra (Figure S1). Infrared spectroscopy The IR spectra of the free L ligand exhibits a C=S stretching vibration at 532 cm -1. The thione band (C=S) is shifted to 507, 519, 512, 520, 509 and 509 cm-1 for compounds 16, respectively. The observed absorption band at 1392 cm-1 for 1 is assigned to the υ3(É ) of the nitrate ion.91 The strong bands which appear at the region of 639 and 1030 cm-1 and also the broad bands at 1163, 1283 and 1256 cm-1 for polymer 2 can be assigned to the stretching vibrations of the triflate anion.92, 93 It is worth to note that three coordination modes of the triflate anion (monodendate, µ-O,O′ bridging and counter ion) have been found in this compound. In the network of 3, the observed absorption band extending from 1039 to 1160 cm-1 (υ3(T2) and 1030 to 1420 cm-1 are assigned for the perchlorate and nitrate anions, respectively.91 In the tetrafluoroborate containing complex of 4, a broad peak at 1013- 1130 cm-1 (υ1(A1)) indicates the presence of BF4− anion in the complex 94,91 , while a peaks at 1386 cm-1 confirms the presence of the NO3− anion.95 .In the IR spectrum of compound 5, a peak at 560 cm-1 and a broad band at 842 cm-1 are assigned to the υ4(T1u) and υ3(T1u) vibrations of the PF6− , respectively.96–97 A peak at 662 cm-1 is assigned to the υ3(T1u) vibration of SbF6-. The


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IR spectrum of coordination polymers 5 and 6 shows a band at 1384 cm-1 that is assigned to the NO3− anion. 96–97 Structural comparison between the coordination polymers 1-6 by a competition between the nitrate ion and co-anions CF3SO3−, ClO4−, BF4−, PF6− and SbF6− Table 3 summarizes the basic structural parameters and features for coordination polymers with structurally related dithioe ligand (chart 1), which helps to explore the impact of competition between the nitrate ion and co-anions CF3SO3−, ClO4−, BF4−, PF6− and SbF6− on the structure of coordination polymers. The single crystal of 1 was obtained by the reaction of S,S′-ditopic ligand with silver nitrate in a mixture of methanol and water (75%, v/v) with branched tube method. This compound was prepared as a reference in order to investigate the competition between the nitrate and the other selected co-anions. [Ag2-ligand]2+n polymeric layer of 1 was produced in the presence of strongly coordinating anion (NO3−). In this case, the anions are only involved in the coordination sphere of AgI. In contrast to the mentioned reactions, polymer 2 was obtained by the reaction of a mixture of of two silver salts (AgNO3 and AgCF3SO3) with the L building block under the same experimental conditions. In this preparation, there is a competition between the coordination ability of the nitrate and triflate anions. Despite of coordination ability expected for both anions, but there is no any evidence to confirm the coordination of these anions simultaneously to the silver atoms. This observation can be rationalized by the fact that the product of the reaction 2 depends highly on the methanol/water ratio and solubility of the silver salts in this solvent. The solubility of the AgCF3SO3 in methanol is much higher than that of the AgNO3, therefore it is more chance for the CF3SO3- anion to coordinate to a silver center than the NO3- anion. While for silver nitrate the solubility in water is higher than that of methanol. In this case, compound 1 has a more chance to be extracted. Thus, compound 2 was obtained in methanol, while in a mixture of methanol/water, a mixture of compounds 1 and 2 were obtained. In this mixture, the percentage of polymer 2 was increased by increasing the amount of methanol in the solvent. To generate structure with a mixed anion, the molar ratio of AgNO3 / AgCF3SO3 and methanol/water were modified, but in each case the obtained result was the same as in 2 or 1. It is worth to note that in the absent of AgNO3 polymer 2 can also be synthesized by the reaction of L ligand with AgCF3SO3. Overall, a mixed-anion complex could be obtained when the solubility of the non silver co-salt be equal or greater than the main silver salt. As in the structure of 1, in 2, anions do not play a role in the formation of polymeric network. The main difference between their topology was related to the variation of coordination mode 19 ACS Paragon Plus Environment


of ligand used in these complexes. When NaClO4 was used instead of AgCF3SO3 to react with L, complex 3 was formed which is composed of an extended cation layer of [Ag2LNO3]+n and ClO4−. In the formation of complex 3, there is a competition between the coordination ability of nitrate and perchlorate anions. In polymer 3, nitrate and perchlorate anions act as coordinated and uncoordinated, respectively. The 2D structure of 3 is isostructural with {[Ag2LNO3][BF4]}n (4). As in the structure of 1 and 3, in 4 the ligand acts as a hexadentate bridging ligand with coordination mode of bis-µ3 bridging, however the conformation of ligand in 1 is anti while in 3 and 4 are syn. The non-coordinating BF4− and weakly coordinating ClO4− anions were observed as a guest in the [Ag2LNO3]+n layer structures. Structural analysis between the 2D ionic compounds 3 and 4 and the 2D neutral structure of 1 as base compound, was demonstrated that the counter ions BF4− and ClO4− have a notable impact in directing the conformation of ligand and coordination fashion of nitrate anion, but they have no effect on the coordination mode of the ligand. Furthermore, by the influence of these counter anions the Ag…Ag distances in the distorted square Ag2S2 rings were twice shorter than the van der Waals radii of the silver(I) ion (3.4 Å). This observation, suggesting the existence of significant argentophilic interactions. In the basic isostructural compounds 1, 3 and 4, with anions of weaker coordination ability, the sum of the S-Ag-S angles around the AgI atoms [ 279.79(for 1), 343.33(for 2) and 345.69(for 3)] were increased and the structure of [Ag2L]2+n became more planar. In order to further evaluate the influence of counter anions on the structure of the complexes and follow the competition between them and nitrate, PF6− was used as a co-anion to react with thione ligand. In this case, complex 5 was formed which is constructer from cationic chain [Ag2LNO3]

+ n

and PF6−. X-ray diffraction shows that in contrast to the polymeric chain of 2

in the structure of 5, coordination mode of the ligand is just chelating combining bis µ2bridging but similar to 3 and 4, both anions appear in the structure. When PF6− anions were involved, a type of double-stranded polymeric chain was noted. In this structure compared to the other structures listed afore, both the nitrate anions and the ligands were involved in the formation of 1D-coordination network with AgI. In fact, change the type of co- anion modified by changing the coordination mode of the nitrate anion and ligand and hence cause a change in the structural dimension of the polymer. PF6− and SbF6− are similar, thus we have prepared polymer 6 with SbF6− without expecting much structural changes. However, only a small modification between the structures 5 and 6 was observed. In polymer 5, each of the nitrate ions is linked to three silver atoms while in 6 one nitrate anion bridging two silver atoms with a tridentate coordination mode. Structural comparison between the understudy 20 ACS Paragon Plus Environment

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polymers based on the 1- 3- bis (1-methylthioimidazolyl) propane can be rationalized by the fact that the co- anions predominantly used as counter ion while nitrate anion coordinated to the silver center as a co-ligand with different coordination modes. In general, the effect of anions on the framework of the considered polymers can be explained on the basis of their differences in size and coordination ability. The differences of coordination abilities of anions greatly influence the coordination and linkage modes of the ligand and nitrate anion to result in different structure networks. In the meantime, a significant increase in Ag···Ag interactions occurred by decreasing the coordination ability of the anions. From this systematic investigation of the coordination polymer architectures based on the self-assembly of the bis (2-thione) ligands and Ag(I) centers, we concluded that two parameters play a major role in the structures of coordination polymers: the flexibility of ligand and the coordinating

ability

of


the

anions.

Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46

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Table 3. Structural comparison of Ag(I) polymers with 1- 3- bis ( 1-methylthioimidazolyl) propane ligand. No. Formula

1. [Ag2L3(NO3)2]n

Ligand coord.

Ag–S length and

dimension S…S separation

membered

Modes

Ag–O length (av.)/ Å

structure of ligand and Ag…Ag distance(av.)/ Å

metallomacrocycles

Bis-µ3 bridging

2.638 and 2.427

2D

7.740 and 3.86

20 and 4

a-a

[Ag2L]2+n

Tetrahedral, trigonal

Chelating combining 2.548 and 2.462

1D

4.645 and 3.04

4, 5 , 6, 8

g-a

[Ag6L4]4+n

pyramidal and trigonal planar

µ2 and µ3-bridging,

(AgS3O, and AgS2O AgS3)

Chelating combining

Ag(I) Geometry

trigonal bipyramidal

conformation

backbone Structure

(AgS3O2) 3

2. {[Ag6L 4(CF3SO3)4][CF3SO3]2}n

and 10

Bis µ2-bridging and Bis µ2-bridging 3. {[Ag2L3(NO3)][ClO4]}n

trigonal bipyramidal (AgS3O2)

Bis-µ3 bridging

2.653 and 2.587

2D

5.030 and 3.120

3 and 12

a-a

[Ag2L]2+n

4. {[Ag2L3(NO3)][BF4]}n

trigonal bipyramidal

Bis-µ3 bridging

2.639 and 2.578

2D

4.890 and 3.013

3 and 12

a-a

[Ag2L]2+n

T- shape and seesaw

Chelating combining 2.482 and 2.604

1D

4.938 and 3.120

3 and 6 and 10

a-a

[Ag2LNO3]+n

(AgS2O and AgS2O2)

Bis µ2-bridging

T- shape and seesaw (AgS2O and AgS2O2)

Chelating combining 2.493 and 2.644 Bis µ2-bridging

1D

4.948 and 3.120

3 and 6 and 10

a-a

[Ag2LNO3]+n

(AgS3O2) 5. {[Ag2L3(NO3)][PF6]}n

6. {[Ag2L3(NO3)][SbF6]}n


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Thermal analysis To characterize thermal stabilities of compounds 1–6, their thermal decomposition behaviors were investigated by the TGA (Figure 7). The experiments were performed under Argon atmosphere at a heating rate of 10˚C min-1 in the temperature range of 20- 900˚C. The combustion of the flexible ligand and destruction of the framework of these polymers start at temperature range of 140-328˚C. On the basis of the TGA data it can be concluded that polymer 2 has more thermal stability than the other title compounds which have lower decomposition temperature than 2. Compound 1 decompose in a two-step process at the range of 140 to 402˚C which corresponding to the burning of flexible ligand and part of the nitrate anions. Compound 2 exhibits a one-step decomposition curve which start at about 328˚C and completed at 500˚C. The weight loss of 2 assigned to the decomposition of the L ligand and two moles of the triflate anions. Polymers 3 and 4 were thermally more stable than 1, because in the 2D-coordination network structures of 3 and 4 silver atoms are simultaneously joint together by means of the anions and ligands which would reinforce each other in the direction of the structure. Polymers 3 and 4 decompose in two step due to the combustion of the ligand and nitrate anions. Compound 5 exhibits a three-step degradation spectrum in the range of 140 and 382˚C consistent to the removal of the ligand and one mole of the hexafluorophosphate anion. The TGA curve of 6 exhibits a two-step degradation between 145 and 316 ˚C corresponding to the combustion of ligand and one mole of the hexafluoroantimonate anion.



Figure 7. The TGA curves of the coordination polymers 1-6 recorded at heating rate of 10 ˚C /min.

Photo physical properties The UV–Vis spectra of the flexible thione ligand along with its complexes were recorded in methanol. As illustrated in Figure 8, the electronic spectrum of the flexible thione ligand displays a sharp band at 246 nm which can be assigned to the π → π* transitions in the C=S group of the 1-methylimidazoline- 2(3 H)-thione rings of the ligand. In the spectra of the considered polymers, this band is slightly red-shifted to 253 (for 1), 269 (for 2), 257 (for 3), 258 (for 4), 264 (for 5) and 265 nm (for 6) upon coordination of the flexible thione ligand to the AgI ions via sulphur atoms.


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2 Ligand Polymer 1 Polymer 2

1.6

Polymer 3 Polymer 4 Polymer 5

1.2

polymer 6

Absorbance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.8

0.4

0 200

300

400

500

Wavelength

Figure 8. The UV–Vis spectra of the flexible thione ligand with its complexes in methanol.

Ag(I) complexes can emit weak photoluminescence at low temperatures and only a few number of papers have been appeared in the literature which deals with the luminescent properties of these compounds.102 As depicted in Figure 9, in the solid state polymers 1-6 exhibited a blue fluorescent emission. The emission spectra consist of similar broad emission band in the visible region which extends to around 660 nm. The emission maxima (λmax) is located at 471.2 (for 1), 467.6 (for 2), 469.2 (for 3), 468.8 (for 4), 467.9 (for 5) and 469.3 nm (for 6) (λex 246 nm). Compared with those of the free ligand (468.4 nm), photoluminescence transitions of the title complexes are ligand-based emission and the emission band of 1 is bathochromic, while those of the 2 - 6 are hypsochromic in some sort.



16000

Ligand

14000

Intensity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 45

Polymer 1

12000

Polymer 2

10000

Polymer 3

8000

Polymer 4

6000

Polymer 5

4000

Polymer 6

2000 0 300

400

500

600

700

Wavelentgh Figure 9. Solid- state emission spectra of the ligand and considered coordination polymers at room temperature.

Antibacterial activity assay Table S2 presents the antibacterial results of the free ligand and its silver polymers. On the basis of these results, all the tested coordination polymers possess a broad spectrum of antibacterial activity against both Gram-positive and Gram-negative target bacteria. These results also confirmed that the inhibition ability of polymers 1-6 is higher than that of the free ligand. As can be found all the tested complexes were potent antibacterial agents and inhibited bacterial growth even at lowest concentration used in Kirby- Bauer disc diffusion test. There was no significant difference in susceptibility of Gram positive and Gram negative bacteria to tested complexes. The results of MIC and MBC indices also confirmed the high inhibitory effect of the synthesized complexes. The MIC and MBC of all complexes against four bacterial species was 0.5 mg/ml. These data suggest that the considered complexes are mostly bactericidal agents that can kill target bacteria at low concentration. The high antibacterial potential of these complexes is due to the presence of AgI in the structure of complexes. This ion can effectively bind with vital enzymes of bacterial cell that are involved in cell wall synthesis, degradation of macromolecules, polymerization of building blocks and assembly of bacterial structures. Therefore, simultaneously cell growth, division, and metabolic pathways of bacterial cell will be affected and hence the bacterial death is the consequence of encountering of bacteria with these complexes. Furthermore, complexes can disrupt cell membrane integrity due to their entrance into bilayer phospholipid membrane of 26 ACS Paragon Plus Environment

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bacterial cell and increasing its fluidity. As a consequence of increasing membrane fluidity phospholipid packaging will be reduced and all of the biological activities that are dependent to cell membrane will be disrupted and retardation in bacterial growth and bacterial killing will be resulted. Conclusion Six new silver(I)-based coordination polymers of the 1, 3- bis (1-methylthioimidazolyl) propane ligands with a variable coordination mode of ligand and nitrate anion have been synthesized by a competition between the nitrate ion and co- anions CF3SO3−, ClO4−, BF4−, PF6− and SbF6−. On the basis of the obtained results it was found that in a competition between the nitrate ion and other anions, the non-coordinating anions BF4−, PF6− and SbF6− and weakly coordinating ClO4− directed toward the synthesis of the under study cationic coordination polymers with two kind of anions, while moderately coordinating anion CF3SO3− build up a cationic structure with only one kind of anion. The differences between the coordination ability of the co- anions can be considered as the most effective factor for determining the coordination and linkage modes of the ligand and nitrate anion and hence to construct different coordination polymers with variable structural topologies. The TGA experimental data reveal that polymer 2 has more thermal stability than the other title compounds. In the electronic spectrum of the considered polymers, sharp band at 246 nm of ligand is slightly red-shifted upon coordination of the flexible thione ligand to the AgI ions via sulphur atoms. All of the synthesized compounds display a strong blue emission in the solid state at room temperature. Apart from interesting structural and topological features, these compounds exhibited a significant antibacterial activity. Acknowledgement We thank Shahid Chamran University of Ahvaz for financial support (grant number: 95/3/02/31400). Appendix A. Supplementary material CCDC reference numbers 1850251(1), 1850253(2), 1850252(3), 1858741(4), 1850254(5), 1850255(6) contains the supplementary crystallographic data for compounds 1-6. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif.



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