Synthesis and characterization of trimeric phosphazene based ionic liquids with tetrafluoroborate anions and their thermal investigations

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Synthesis and characterization

of trimeric phosphazene based

ionic liquids with tetrafluoroborate

anions and their thermal

investigations

Ahmet Karadağ

1*

_{, Hüseyin Akbaş}

2

_{, Ali Destegül}

2

_{, Çiğdem Çakırlar}

3

_{, Yusuf Yerli}

4

_,

Zeynel Kılıç

5

_{& fatih Sen}

6*

The quaternized compounds (PzIL1–9) reacted with sodium tetrafluoroborate (NaBF4) to generate

phosphazene based ionic liquids (PzILs), PzIL1a–9a. The newly synthesized ionic compounds (PzIL1a–9a) were verified using elemental CHN analyses and functional and spectroscopic (FTIR and 1_H,13_c,31_{P-NMR) analyses techniques. The thermal properties of PzIL1a–9a were investigated}

using thermogravimetric analysis (TGA). According to the initial decomposition temperature values calculated based on the TGA thermograms, PzIL7a (213 °C) was recognized to be more thermally stable than the other PzILs studied. PzIL1a–9a exhibited good solubility in the water and demonstrate a typical dielectric relaxation behavior, conductivity levels for both low and high-frequency regions. AC conductivity mechanisms and dielectric relaxation behavior of each sample are investigated by fabricating parallel plate capacitors.

The nucleophilic substitution reactions of phosphazenes are well known1–3_{. Thus, a broad array of poly and} cyclophosphazene derivatives were obtained. Nevertheless, PzILs obtained by the quaternization of the skeletal or the side-group nitrogen atoms of phosphazene have received much less attention4_{. Compounds formed by} the protonation of the ring nitrogen atom of the cyclophosphazenes are defined as protic molten salts (PMOSs) or protic ionic liquids (PILs)5,6_{. Protonation of the ring nitrogen with various acids was carried out, and the} protonation was first determined by infrared and NMR methods7,8_{. In later years, the crystal structures of} N3P3Cl2(NHPri)4·HCI and [N3P3HCl4(NH2)2]+[N(POCl2)2]− were determined by X-ray analysis9,10. Tun and

col-leagues observed two types of products, reacting with N3P3Cl6 and group 13 Lewis acids.[PCl2N]3·MX3 obtained

by excluding water or HX is the main product. Whenever MX3 (AlCl3, GaCl3, AlBr3) was used, water traces

were always found, and by isolating [PCl2N]3·HMX4 (HMX4: HAlCl4, HGaCl4, HAlBr4) structures as the second

product, they detected the location of the protonation by X-ray crystallography11,12_{. In recent years, PILs have} been synthesized using a variety of cyclophosphazene compounds and bulky acids (salicylic, gentisic, γ-resorcylic acids), and the biological activity of these PMOSs has been investigated13–15_{. In addition to these, phosphazenes} containing aliphatic and aromatic substituents having terminal tertiary amino groups were synthesized and then quaternized with methyl iodide16–21_{. The PzILs with different anions (chloride, Cl}−_{, bis-trifluoromethane}

sulfon-imide, NTf2− and tetrafluoroborate, BF4−) were obtained by simple anion exchange reactions17,20–25. On the other

hand, PzILs with various molecular weights or different average chain lengths have been used as antibacterial, antifungal and anticancer agents5,6,13–15_{, lubricants}17,25_{, adsorbents and surface modifiers}18_{, a gate dielectric layer} for OFETs20,21_{, electrolyte solutions}19,23,24_{and chemosensors for metal ions}26_.

open

1_{Department of Chemistry, Faculty of Arts and Sciences, Yozgat Bozok University, 66200 Yozgat,} Turkey. 2_{Department of Chemistry, Faculty of Arts and Sciences, Gaziosmanpaşa University, Tokat,} Turkey. 3_{Department of Physics, Gebze Technical University, Kocaeli, Turkey.}4_{Department of Physics, Yıldız} Technical University, Istanbul, Turkey. 5_{Department of Chemistry, Ankara University, Ankara, Turkey.}6_Department of Biochemistry, University of Dumlupınar, Kütahya, Turkey. *_{email: ahmet.karadag@bozok.edu.tr; fatih.sen@}

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Especially, FETs with a metal oxide dielectric layer suffer from high-temperature fabrication processes, high operating voltages, limited flexibility, etc. While ILs offer many advantages with smaller sizes, fast operation speed, reduced power requirements (< 1 V), and reduced heat production27_{. It is essential to investigate their} elec-trical properties to find out their potential applications28_{. Higher ionic conductivity values and higher dielectric} permittivity are expected for any of ILs due to the ionic migration and double-layer formation29_.

The present study focuses on the preparation of PzILs containing tetrafluoroborate anions by anion exchange reaction (Scheme 1). The purpose of these syntheses of the PzILs (PzIL1a–9a) is to confirm the spectroscopic and thermal properties, electrical conductivities and dielectric behaviors, and to check against these obtained results with those of the PzILs containing the I−_{and NTf}

2− anions in the literature20,21.

Experiment

Materials.

4-Fluorobenzaldehyde, aliphatic amines (N-methyl-ethylenediamine, N-ethyl-ethylenediamine, and N-methyl-1,3-diamino propane), amino alcohols (2-dimethylaminoethanol, 3-dimethylamino-1-propanol, and 4-pyridinemethanol), methyl iodide, sodium tetrafluoroborate, hexachlorocyclotriphosphazene (recrystal-lized from hexane), and organic solvents were obtained commercially (Sigma-Aldrich). The organic solvents were dried and distilled by common methods before use. Sodium {rod diameter 2.5 cm (protective liquid: paraf-fin oil)} was purchased from Merck.

Measurements.

Elemental analyses (C, H, N) were performed using a LECO CHNS-932 elemental ana-lyzer. The Fourier transform infrared (FTIR) spectra of all the PzILs were monitored with a Jasco 430 FT-IR Spectrometer in KBr pellets in the 4,000–400 cm−1_region.1_H,13_C{1_{H}, and}31_P{1_{H} NMR spectra were recorded}

on Agilent 600 MHz Premium COMPACT NMR spectrometer (tetramethylsilane (TMS) as an internal standard for 1_{H and 85% H}

3PO4 as an external standard for 31P NMR), operating at 600, 151 and 243 MHz. The thermal

analyses were performed on Perkin Elmer Diamond TG/DTA Thermal Analysis Instrument with a heating rate of 10 °C min−1_{and 5–10 mg sample in a nitrogen atmosphere.}

Synthesis.

The notations of the general formulae of the PzILs are given as [Px2Pyy3N][X]4 {x:1, R:(CH2)2,

Rʹ:(CH3); x:2, R:(CH2)2, Rʹ:(C2H5); x:3, R:(CH2)3, Rʹ:(CH3); y:1, O(CH2)2N(CH3)3+; y:2, O(CH2)3N(CH3)3+; y:3,

OCH2PhNCH3+; X: I− or BF4−} (Scheme 1). Free cyclotriphosphazene bases and cyclic trimers fully substituted

by aliphatic and aromatic substituents with terminal tertiary amino functions have been synthesized and sub-sequently quaternized by treatment with methyl iodide. The quaternized derivatives (PzIL1–9) were obtained according to published papers20,21_.

F _N N R' N P N P N P N O N O N O N O F _N _{N R'} N P N P N P O N O N N O N O F N N R' N P N P N P O O O O N N N N I I I I I I I I I I F N N R' N P N P N P N O N O N O N O F _N N R' N P N P N P O N O N N O N O F _N _{N R'} N P N P N P O O O O N N N N

NaBF4 NaBF4 NaBF4

( R ₎ ( R ₎ ( R ₎ ( R ₎ ( R ₎ ( R ₎ R Compound PzIL1 PzIL4 CH3 CH2CH3 R' (CH2)2 (CH2)2 (CH2)3 CH3 PzIL7 BF4 BF4 BF4 BF4 BF4 BF4 BF4 BF4 BF4 BF4 BF4 BF4 12 34 5 6 7 8 9 10 11 I I PzIL2 PzIL5 CH3 CH2CH3 (CH2)2 (CH2)2 (CH2)3 CH3 PzIL8 PzIL3 PzIL6 CH3 CH2CH3 (CH2)2 (CH2)2 (CH2)3 CH3 PzIL9 PzIL1a PzIL4a CH3 CH2CH3 (CH2)2 (CH2)2 (CH2)3 CH3 PzIL7a PzIL2a PzIL5a CH3 CH2CH3 (CH2)2 (CH2)2 (CH2)3 CH3 PzIL8a PzIL3a PzIL6a CH3 CH2CH3 (CH2)2 (CH2)2 (CH2)3 CH3 PzIL9a x y y R Compound R' Compound R R' R

Compound R' Compound R R' Compound R R'

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Synthesis of [P12P113N][BF4]4.3/2H2O (PzIL1a). To a stirring aqueous solution of PzIL1 (1.00 g, 0.8 mmol)

was added 4.0 mol equivalent of sodium tetrafluoroborate (NaBF4) (0.35 g, 3.2 mmol) dissolved in water and the

reaction mixture was warmed at 40 °C for 1 h. However, PzIL1a was water soluble and the crude solution mixture was evaporated to dryness. The desired product was extracted with acetone17_{. Yield: 0.58 g (65.2%). FTIR (KBr,} cm−1_{): ν 3,435 (–OH); 3,051 (C–H arom.); 3,009 (N(CH}

3)3+); 2,969, 2,880 (C–H aliph.); 1604, 1509 (C=C arom.);

1,222, 1,148 (P=N); 1,092 (C–F); 1,045 (B–F); 972 (P–O–C). 1_{H NMR (DMSO, ppm, numberings of protons are}

given in Scheme 1): δ 7.21 (dd, 2H, 3_J

FH = 8.8 Hz, H2 and H6), 7.43 (dd, 2H, 3JHH = 8.5 Hz, 4JFH = 5.7 Hz, H3 and

H5), 3.93 (d, 2H, 3JPH = 9.5 Hz, ArCH2N), 3.03 (m, 2H, NCH2), 2.91 (m, 2H, CH2NR), 2.47 (d, 3H, 3JPH = 9.5 Hz

NCH3), 4.33 (m, 8H, POCH2), 3.71 (m, 8H, POCH2CH2), 3.13 (m, 36H, N(CH3)3+). 13C NMR (DMSO, ppm,

numberings of carbons are given in Scheme 1): δ 161.39 (1_J

FC = 242.8 Hz, C1), 115.21 (2JFC = 21.3 Hz, C2 and C6),

129.79 (3_J

FC = 8.2 Hz, C3 and C5), 134.00 (3JPC = 7.5 Hz, C4), 46.74 (2JPC = 10.6 Hz, ArCH2N), 43.45 (2JPC = 12.4 Hz,

NCH2), 42.91 (2JPC = 12.4 Hz, CH2NR), 31.44 (2JPC = 4.0 Hz, NCH3), 54.39 (POCH2), 64.61 (POCH2CH2), 53.15

(N(CH3)3+). Anal. Calcd for C30H68B4F17N9O5.5P3: C, 32.7; H, 6.2; N, 11.4 Found: C, 32.3; H, 5.8; N, 11.0.

Synthesis of [P12P223N][BF4]4·1/2H2O (PzIL2a). Compound PzIL2a was prepared from PzIL2 by the same

procedure described for PzIL1a. Yield: 0.60 g (68.9%). FTIR (KBr, cm−1_{): ν 3,535 (–OH); 3,054 (C–H arom.);}

3,009 (N(CH3)3+); 2,961, 2,875 (C–H aliph.); 1604, 1509 (C=C arom.); 1,228, 1,177 (P=N); 1,086 (C–F); 1,049

(B–F); 972 (P–O–C). 1_{H NMR (DMSO, ppm, numberings of protons are given in Scheme}₁_{): δ 7.22 (dd, 2H,} 3_J

FH = 8.8 Hz, H2 and H6), 7.45 (dd, 2H, 3JHH = 8.4 Hz, 4JFH = 5.7 Hz, H3 and H5), 3.93 (d, 2H, 3JPH = 10.7 Hz,

ArCH2N), 3.09 (m, 2H, NCH2), 2.89 (m, 2H, CH2NR), 2.46 (d, 3H, 3JPH = 10.7 Hz NCH3), 3.48 (m, 8H, POCH2),

1.83 (m, 8H, POCH2CH2), 3.36 (m, 8H, POCH2CH2CH2), 3.06 (m, 36H, N(CH3)3+). 13C NMR (DMSO, ppm,

FC = 244.9 Hz, C1), 115.18 (2JFC = 21.3 Hz, C2 ad C6),

129.67 (3_J

NCH2), 43.49 (2JPC = 12.1 Hz, CH2NR), 31.38 (2JPC = 3.4 Hz, NCH3), 57.64 (POCH2), 25.66 (POCH2CH2), 63.62

(POCH2CH2CH2), 52.21 (N(CH3)3+).Anal. Calcd for C34H74B4F17N9O4.5P3: C, 35.8; H, 6.5; N, 11.1 Found: C,

35.4; H, 6.1; N, 11.4.

Synthesis of [P12P333N[BF4]4.3H2O (PzIL3a). Compound PzIL3a was prepared from PzIL3 by the same

pro-cedure described for PzIL1a. Yield: 0.49 g (62.0%). FTIR (KBr, cm−1_{): ν 3,485 (–OH); 3,043 (C–H arom.); 3,009}

(PhNCH3+); 2,927, 2,862 (C–H aliph.); 1604, 1509 (C=C arom.); 1,221, 1,189 (P=N); 1,084 (C–F); 1,035 (B–F);

948 (P–O–C). 1_{H NMR (DMSO, ppm, numberings of protons are given in Scheme}₁_{): δ 7.21 (dd, 2H,}3_J

FH = 8.8 Hz,

H2 and H6), 7.43 (dd, 2H, 3JHH = 8.5 Hz, 4JFH = 5.7 Hz, H3 and H5), 3.93 (d, 2H, 3JPH = 9.5 Hz, ArCH2N), 3.03 (m,

2H, NCH2), 2.91 (m, 2H, CH2NR), 2.47 (d, 3H, 3JPH = 9.5 Hz NCH3), 4.27 (m, 8H, POCH2), 8.82 (dd, 8H, H7 and

H11), 8.06 (dd, 8H, H8 and H10), 4.32 (m, 36H, N(CH3)+). 13C NMR (DMSO, ppm, numberings of carbons are

given in Scheme 1): δ 161.49 (1_J

FC = 243.3 Hz, C1), 115.26 (2JFC = 21.4 Hz, C2 and C6), 129.73 (3JFC = 8.0 Hz, C3 and

C5), 134.04 (3JPC = 6.5 Hz, C4), 47.08 (2JPC = 6.5 Hz, ArCH2N), 48.02 (2JPC = 12.1 Hz, NCH2), 44.31 (2JPC = 12.1 Hz,

CH2NR), 30.88 (2JPC = 3.5 Hz, NCH3), 61.19 (POCH2), 128.70 (C7 and C11), 124.72 (C8 and C10), 145.09 (C9);

50.57 (N(CH3)+). Anal. Calcd for C38H53B4F17N9O6P3: C, 38.3; H, 4.5; N, 10.6 Found: C, 38.00; H, 4.0; N, 10.6.

Synthesis of [P22P113N][BF4]4H2O (PzIL4a). Compound PzIL4a was prepared from PzIL4 by the same

ArCH2N), 3.06 (m, 2H, NCH2), 2.81 (m, 2H, CH2NR), 2.91 (m, 2H, NCH2CH3), 1.11 (t, 3H, 3JHH = 7.1 Hz

NCH2CH3), 4.32 (m, 8H, POCH2), 3.71 (m, 8H, POCH2CH2), 3.16 (m, 36H, N(CH3)3+). 13C NMR (DMSO, ppm,

FC = 243.2 Hz, C1), 115.21 (2JFC = 21.3 Hz, C2 and C6),

129.83 (3_J

NCH2), 43.19 (2JPC = 13.1 Hz, CH2NR), 38.71 (2JPC = 4.3 Hz, NCH2CH3), 13.71 (3JPC = 5.8 Hz, NCH2CH3), 59.74

(POCH2), 64.57 (POCH2CH2), 53.27 (N(CH3)3+). Anal. Calcd for C31H69B4F17N9O5P3: C, 33.6; H, 6.3; N, 11.4

Found: C, 33.7; H, 6.0; N, 11.2.

Synthesis of [P22P223N][BF4]4·H2O (PzIL5a). Compound PzIL5a was prepared from PzIL5 by the same

pro-cedure described for PzIL1a. Yield: 0.58 g (69.9%). FTIR (KBr, cm−1_{): ν 3,506 (–OH); 3,040 (C–H arom.); 3,009}

(N(CH3)3+); 2,960, 2,873 (C–H aliph.); 1604, 1509 (C=C arom.); 1,221, 1,148 (P=N); 1,080 (C–F); 1,051 (B–F);

960 (P–O–C). 1_{H NMR (DMSO, ppm, numberings of protons are given in Scheme}₁_{): δ 7.22 (dd, 2H,}3_J

FH = 8.7 Hz,

H2 and H6), 7.45 (dd, 2H, 3JHH = 7.8 Hz, 4JFH = 5.6 Hz, H3 and H5), 3.90 (d, 2H, 3JPH = 9.2 Hz, ArCH2N), 3.08 (m,

2H, NCH2), 2.90 (m, 2H, CH2NR), 3.01 (m, 2H, NCH2CH3), 1.12 (t, 3H, 3JHH = 7.8 Hz NCH2CH3), 3.95 (m, 8H,

POCH2), 1.83 (m, 8H, POCH2CH2), 3.48 (m, 8H, POCH2CH2CH2), 3.06 (m, 36H, N(CH3)3+). 13C NMR (DMSO,

ppm, numberings of carbons are given in Scheme 1): δ 161.45 (1_J

FC = 242.4 Hz, C1), 115.20 (2JFC = 21.2 Hz,

C2 and C6), 129.70 (3JFC = 7.9 Hz, C3 and C5), 132.62 (3JPC = 6.4 Hz, C4), 47.04 (2JPC = 6.5 Hz, ArCH2N), 43.75

(2_J

PC = 12.5 Hz, NCH2), 43.50 (2JPC = 12.5 Hz, CH2NR), 38.71 (2JPC = 5.2 Hz, NCH2CH3), 13.64 (3JPC = 5.5 Hz,

NCH2CH3), 57.66 (POCH2), 25.66 (POCH2CH2), 63.64 (POCH2CH2CH2), 52.23 (N(CH3)3+). Anal. Calcd for

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Synthesis of [P22P333N][BF4]4·2H2O (PzIL6a). Compound PzIL6a was prepared from PzIL6 by the same

3,009 (PhNCH3+); 2,972, 2,871 (C–H aliph.); 1605, 1509 (C=C arom.); 1,222, 1,186 (P=N); 1,083 (C–F); 1,051

FH = 8.7 Hz, H2 and H6), 7.43 (dd, 2H, 3JHH = 7.8 Hz, 4JFH = 5.8 Hz, H3 and H5), 3.93 (d, 2H, 3JPH = 7.8 Hz, ArCH2N),

3.06 (m, 2H, NCH2), 2.81 (m, 2H, CH2NR), 2.91 (m, 2H, NCH2CH3), 1.11 (t, 3H, 3JHH = 7.1 Hz NCH2CH3), 4.27

(m, 8H, POCH2), 8.82 (dd, 8H, H7 ve H11), 8.06 (dd, 8H, H8 ve H10), 4.32 (m, 36H, N(CH3)+). 13C NMR (DMSO,

FC = 243.1 Hz, C1), 115.27 (2JFC = 21.3 Hz,

C2 and C6), 129.77 (3JFC = 8.1 Hz, C3 and C5), 134.03 (3JPC = 6.8 Hz, C4), 46.71 (2JPC = 6.0 Hz, ArCH2N), 43.47

(2_J

PC = 13.1 Hz, NCH2), 43.19 (2JPC = 13.1 Hz, CH2NR), 38.60 (2JPC = 4.7 Hz, NCH2CH3), 13.62 (3JPC = 5.7 Hz,

NCH2CH3), 61.17 (POCH2), 128.70 (C7 and C11), 124.72 (C8 and C10), 145.09 (C9); 50.57 (N(CH3)+). Anal. Calcd

for C39H55B4F17N9O6P3: C, 38.9; H, 4.6; N, 10.5 Found: C, 39.3; H, 4.3; N, 10.9.

FH = 8.7 Hz, H2 and H6), 7.40 (dd, 2H, 3JHH = 7.8 Hz, 4JFH = 5.7 Hz, H3 and H5), 3.90 (d, 2H, 3JPH = 8.3 Hz, ArCH2N),

3.11 (m, 2H, NCH2), 1.68 (m, 2H, NCH2CH2), 2.91 (m, 2H, CH2NR), 2.46 (s, 3H, NCH3), 4.29 (m, 8H, POCH2),

3.67 (m, 8H, POCH2CH2), 3.16 (m, 36H, N(CH3)3+). 13C NMR (DMSO, ppm, numberings of carbons are given

in Scheme 1): δ 161.49 (1_J

FC = 242.9 Hz, C1), 115.24 (2JFC = 21.3 Hz, C2 and C6), 129.74 (3JFC = 8.1 Hz, C3 and C5),

134.40 (3_J

PC = 9.5 Hz, C4), 49.76 (ArCH2N), 48.80 (NCH2), 23.59 (NCH2CH2), 45.84 (CH2NR), 35.25 (NCH3),

59.70 (POCH2), 64.61 (POCH2CH2), 53.21 (N(CH3)3+). Anal. Calcd for C31H72B4F17N9O6.5P3: C, 32.8; H, 6.4; N,

11.1 Found: C, 33.0; H, 6.2; N, 10.9.

FH = 9.0 Hz, H2 ve H6), 7.40 (dd, 2H, 3JHH = 8.3 Hz, 4JFH = 5.9 Hz, H3 ve H5), 3.93 (d, 2H, 3JPH = 8.3 Hz, ArCH2N),

3.11 (m, 2H, NCH2), 1.67 (m, 2H, NCH2CH2), 2.87 (m, 2H, CH2NR), 2.46 (s, 3H, NCH3), 4.78 (m, 8H, POCH2),

1.83 (m, 8H, POCH2CH2), 3.48 (m, 8H, POCH2CH2CH2), 3.06(m, 36H, N(CH3)3+). 13C NMR (DMSO, ppm,

FC = 243.0 Hz, C1), 115.22 (2JFC = 21.6 Hz, C2 ve C6),

129.89 (3_J

FC = 7.9 Hz, C3 ve C5), 134.85 (3JPC = 5.6 Hz, C4), 49.81 (ArCH2N), 48.86 (NCH2), 22.87 (NCH2CH2),

45.85 (CH2NR), 34.79 (NCH3), 57.65 (POCH2), 25.66 (POCH2CH2), 63.64 (POCH2CH2CH2), 52.23 (N(CH3)3+).

Anal. Calcd for C35H78B4F17N9O5.5P3: C, 33.4; H, 6.3; N, 11.3 Found: C, 32.9; H, 6.1; N, 10.8.

Synthesis of [P32P333N][BF4]4·4H2O (PzIL9a). Compound PzIL9a was prepared from PzIL9 by the same

3,009 (PhNCH3+); 2,951, 2,871 (C–H aliph.); 1605, 1508 (C=C arom.); 1,219, 1,189 (P=N); 1,083 (C–F); 1,053

ArCH2N), 3.11 (m, 2H, NCH2), 1.68 (m, 2H, NCH2CH2), 2.91 (m, 2H, CH2NR), 2.46 (s, 3H, NCH3), 4.27 (m,

8H, POCH2), 8.82 (dd, 8H, H7 and H11), 8.06 (dd, 8H, H8 and H10), 4.32 (m, 36H, N(CH3)+). 13C NMR (DMSO,

FC = 242.9 Hz, C1), 115.24 (2JFC = 21.3 Hz, C2

and C6), 129.74 (3JFC = 8.1 Hz, C3 and C5), 134.40 (3JPC = 9.5 Hz, C4), 49.76 (ArCH2N), 48.80 (NCH2), 23.59

(NCH2CH2), 45.84 (CH2NR), 35.25 (NCH3), 61.18 (POCH2), 128.70 (C7 ve C11), 124.72 (C8 and C10), 145.09

(C9); 50.57 (N(CH3)+). Anal. Calcd for C39H59B4F17N9O8P3: C, 37.7; H, 4.8; N, 10.2 Found: C, 37.3; H, 4.5; N, 9.7.

Dielectric measurements.

The dielectric properties were measured by using a parallel plate capacitor with an impedance analyzer (Hewlett Packard 4194A) in a frequency range between 102_{and 10}7_{Hz. All}

meas-urements were performed at room temperature. To investigate their dielectric properties, all ILs solved in ethyl acetate and ultrasonicated for 30 min to provide a homogeneous solution. ILs were sandwiched by using pre-cleaned Indium tin oxide (ITO) coated glasses. Teflon spacer (t = 0.075 mm) was used to fix the thickness of ILs. The electrode area of all samples has remained the same.

Results and discussion

Syntheses and characterization.

PzILs were prepared by reaction of individual polyiodo ionic com-pounds (PzIL1–9) and NaBF4 aqueous solutions at ambient temperature. However, as PzILs (PzIL1a–9a)

obtained were dissolved in water, the solution mixture was evaporated to dryness and extracted with acetone. PzILs that appeared highly hygroscopic were dried under dynamic vacuum for several days17,20,21_{. However, it} was impossible to keep them in a dehydrated state after exposure to the laboratory and during their transport for chemical analysis. PzILs containing the BF4− anions are soluble in water and very polar organic solvents. We have

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The physical state of ILs with a common phosphazenium cation at 25 °C is usually dependent on anion; for example, compounds containing iodide (I−_{), hexafluorophosphate (PF}

6−), and BF4− as anions are generally

isolated as solids or waxy solids16–18,20,21,30_{. However, in the presence of the NTf}

2− and trifluoromethylsulfonate

(OTf−_{) anions, PzIL s are insoluble in water and are obtained as liquids}17,20,21,30_.

The spin systems and the 31_P{1_{H} NMR data of the PzILs (PzIL1a–9a) are presented in Table}₁_{. The}31_{P spectra}

of PzIL1a, PzIL4a, and PzIL7a are illustrated in Fig. 1, as an example. The 31_{P spectra of the other PzILs were}

analyzed, taking into account of Figs. S1 and S2. The 2_J

PP/Δν values of these compounds are calculated and listed

in Table 1. The average coupling constant, 2_J

PP, value (57.5 Hz) of the PzIL1a–6a (containing the five-membered

spirocyclic ring) is slightly larger than those of the six-membered ones (PzIL7a–9a) (2_J

PP = 53.2 Hz). As expected,

Table 1. 31_P{1_{H} NMR spectral data of the PzILs (PzIL1a–9a). Chemical shifts (δ) are reported in ppm, J}

values in Hz.

Compound δPN(spiro)/PA δP(OR)2/PX 2JPP/Hz Spin sytstem

PzIL1a 27.86 18.48 57.9 AX2 PzIL2a 28.00 18.78 56.7 AX2 PzIL3a 27.91 18.46 58.1 AX2 PzIL4a 26.58 18.51 57.8 AX2 PzIL5a 26.73 18.72 56.2 AX2 PzIL6a 26.47 19.49 58.3 AX2 PzIL7a 22.19 18.00 54.1 AX2 PzIL8a 22.88 18.15 51.7 AX2 PzIL9a 22.26 19.08 53.9 AX2

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PzILs (PzIL1a–9a) have AX2 spin system which give rise to one triplet {PN(spiro)/PA} and one doublet {P(OR)2/

PX}. δP(spiro) (ca. 22.44) of PzIL7a–9a is smaller than those of the PzILs (PzIL1a–6a); δP(spiro) (ca. 27.26). The assignments of the chemical shifts, multiplicities, and coupling constants were elucidated from the 13_C

and 1_{H-NMR spectra (Figs. S3–S14) of the PzILs and presented in “}_Experiment_{” section. The J coupling constants}

and δ shifts of C1, C2/C6, C3/C5, and C4 carbons of the PzILs (PzIL1a–9a) were observed in good agreement with

literature values1,20,21,30_{for the compounds and did not change very much. The average J}

FC and/or JPC values of

C1, C2/C6, C3/C5 and C4 carbons were estimated as 1JFC = 243.2 Hz, 2JFC = 21.3 Hz, 3JFC = 8.0 Hz and 3JPC = 7.2 Hz,

respectively. –N(CH3)3+ signals of the PzILs (PzIL1a–9a) were observed at 52.23–54.21 ppm. –N(CH3)3+ chemical

shifts of the PzIL1a, 2a, 4a, 5a, 7a, and 8a were observed at ~ 52.72 ppm, while the –PhNCH3+ chemical shifts

of the PzIL3a, 6a and 9a have appeared at ~ 50.57 ppm.

On the other hand, the 1_{H NMR data of the PzILs (PzIL1a–9a) were reported in the “}_Experiment_{” section,}

and the expected J coupling constants and δ shift values of hydrogen atoms were elucidated. The 3_J

HH, 3JFH, and 4_J

FH and δ shifts of H2/H6 and H3/H5 protons of the FPh groups of the PzILs (PzIL1a–9a) were interpreted, and

these values were found to be following the literature findings1,20,21,27_{. The average}3_J

HH, 3JFH, and 4JFH values of

H2/H6 and H3/H5 protons of the FPh groups were 3JHH = 8.1 Hz, 3JFH = 8.8 Hz, and 4JFH = 5.7 Hz, respectively.

The Ar-CH2-N protons of the PzILs (PzIL1a–9a) were observed in the range of 3.90–3.93 ppm as doublets.

The average 3_J

PH values of the PzILs (PzIL1a–9a) were calculated as 8.9 Hz. –N(CH3)3+ signals of the PzIL1a,

2a, 4a, 5a, 7a, and 8a were observed at ~ 3.08 ppm, while the –PhNCH3+ signals of the PzIL3a, 6a, and 9a have

appeared at ~ 4.32 ppm.

The νPN bands observed in the ranges of 1,228–1,219 cm−1_{and 1,189–1,124 cm}−1_{, respectively, refer to the} νasymm. and νsymm. stretching vibrations of the P=N bonds of the phosphazene skeletons (Figs. S15–S17)31_{. The} characteristic frequencies of the Ar–H bonds were observed between 3,072 and 3,033 cm−1_{. The νC–F stretching}

bands in the PzILs (PzIL1a–9a) are in agreement with the literature values of the mono fluorinated benzenes 20,21_.

Besides, the νPOC absorption bands of PzILs (PzIL1a–9a) were found to be in the range of 973–945 cm−1_{. The}

characteristic absorption bands in the range of 3,010–3,008 cm−1_{were attributed to the νN(CH}

3)3+ (PzIL1a, 2a,

4a, 5a, 7a, 8a) and νPhNCH3+ (PzIL3a, 6a, 9a) stretching vibrations. Moreover, the presence of the BF4− group

in the PzILs (PzIL1a–9a) was revealed by the νB–F stretching frequency at ~ 1,050 cm−1_.

Thermal studies.

Table S1 gives the details of thermal behavior, according to the primary thermograms (TG) (Fig. 2) and derivative thermograms (DTG) (Fig. S18) for the PzILs (PzIL1a–9a). It can be seen that all the PzILs are decomposed in three steps (Table S1). It is understood that water molecules are separated from the structure in the first step. Most of the mass loss for all compounds occurs in the second step (about 52–93%). In Fig. 2, although there is no visible difference among the decomposition temperatures of ILs, it is seen that the compounds PzIL7a–9a begin to degrade at higher temperatures when Table S1 is examined (213, 189 and 193 °C, respectively). Additionally, we can say that decomposition temperature changes depending on the alkoxy or aryloxy group. The decomposition temperature increases with increased the alkoxy chain length increase for PzIL1a, 2a, and PzIL4a, 5a. For example, PzIL5a begins to decompose at 158 °C, while PzIL4a begins to decompose at 109 °C. But this is not true for PzIL7a and PzIL8a (213, 189 °C, respectively).

When the thermal stability of the PzILs with the same cationic part is compared, it is seen that the ILs con-taining NTf2− anions have higher thermal stability. This is followed by PzILs containing the I− anions and the

BF4− anions, respectively. For example, the decomposition temperature of the PzIL4a (109 °C) is lower than that

of PzILs containing NTf2− anions (292 °C) and I− anions (236 °C) as compared to ILs having the same cationic

part in the literature 20,21_.

Dielectric properties.

Frequency-dependent dielectric permittivity and AC electrical conduction evalu-ation of all samples were investigated. Dielectric response against the time-dependent external electric field is typically given by complex permittivity,

where, ω is angular frequency, ε′ and ε′′ are real and imaginary part of complex permittivity respectively. The

real part of dielectric constant ε′ is attributed to the in-phase polarization and imaginary part, ε′′ represents

out-of-phase polarization called a dielectric loss component. Frequency dependence of the real part of the complex dielectric constant on log-scale is given in Fig. 3a. Real dielectric constant values differ according to the variation of side and the main chain of the samples. The Low-frequency dielectric constant of each sample is very high. Moreover, there is a sharp decrease in dielectric constant with increasing frequency. This phenomenon cannot be associated with a direct molecular motion as for the bulk but attribute the electrode polarization which is due to the diffusion of ions at the interface. Polarization of ILs can be attributed to ion transport and reorientation of dipolar ions. The universal relaxation behavior of ILs is observed for each sample by the spectral measure-ment. ε0 and ε∞ are the static and high-frequency components of the real part of dielectric constant. Relaxation

time (τ(s)) and shape parameter (α) are calculated and given in Table 2. Relaxation time is estimated by using ε′ vs. frequency plots. Also, shape parameter is found by fitting the ε′ vs. frequency plots according to Debye’s

relaxation formula, given in Eq. (2).

(1) ε∗ (ω) = ε′(ω) − iε′′(ω); (2) ε′(ω) = ε∞+(εs−ε∞) 1 + (ωτo)1−αsin1₂απ 1 + 2(ωτo)1−αsin1₂απ + (ωτo)2(1−α)

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The frequency-dependent electrical conductivity variation of each sample is given in Fig. 3b. All newly synthesized ILs have almost the same conductivity behavior; typical electrolyte response. The random barrier model is used to define the charge transport mechanism of ILs. Conductivity mechanism of ILs can be analyzed by using universal law of conductivity; σ(ω) = σ0+ Aωn . Where σ0 and Aωn are DC and AC conductivity

related components respectively, A is a constant and n is the exponent factor. Exponent factor could be varied between 0 to 1 and defines ion-environment interaction for this study. A σ0 and n were estimated by fitting the

bulk properties reflected regions (the region outside of the electrode polarization) according to the universal law. All estimated values are given in Table 2. In high-frequency region hopping conduction exponent factor values vary between 0.72 and 0.92. Hopping conduction region of PzIL2a and PzIL3a is shifted to higher frequencies. This could be attributed to the higher conductivity levels of these samples.

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conclusions

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maintained, have been synthesized and characterized. The different PzILs exhibit different thermal behavior due to structural and functional group differences, but all the PzILs have almost the same thermal decomposition pattern. PzILs with BF4− anions are less stable than PzILs with NTf2− and I− anions. Electrical conductivities and

dielectric behaviors of PzILs were also determined. The static dielectric constant, shape parameter, relaxation time and exponent factor of all newly synthesized ILs were determined using a parallel plate impedance spec-troscopy technique. All samples demonstrate typical conduction behavior of ILs. DC and hopping conduction mechanisms are predominant for each sample. With suitable design, these PzILs can offer unique solutions to a variety of technologies, from the organic field-effect transistor to lithium-ion battery production.

Received: 8 May 2020; Accepted: 29 June 2020

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Table 2. The dielectric parameters of PzILs.

Ionic liquid εs ε∞ τ (s) α σ0 (S/cm) A n

PzIL1a 101 ± 1 80 ± 0.8 1.9E−7 ± 2.5E−8 0 7.2E−6 ± 1.8E−7 4.0E−12 ± 9E−13 0.88 ± 0.01 PzIL2a 57 ± 6 14 ± 0.1 6.5E−7 ± 7.4E−8 0 3.2E−5 ± 5.5E−6 3.2E−5 ± 5.5E−6 0 PzIL3a 205 ± 6 156 ± 1 6.3E−8 ± 9E−9 0 4.7E−4 ± 0 4.7E−4 0 PzIL4a 153 ± 2 104 ± 2 2.2E−7 ± 2.5E−8 0 7.3E−5 ± 8.0E−8 1.7E−12 ± 3.5E−13 0.92 ± 0.01 PzIL5a 36.9 ± 0.8 5.5 ± 0.2 1.2E−6 ± 1.1E−7 0.57 ± 0.01 9.2E−6 ± 1.2E−8 2.6E−11 ± 1.4E−12 0.73 ± 0.003 PzIL6a 18.2 ± 0.3 4.3 ± 0.02 2.4E−6 ± 1.4E−7 0.51 ± 0.005 9.1E−7 ± 4.0E−9 1.5E−11 ± 7.3E−13 0.70 ± 0.002 PzIL7a 31.2 ± 2 4.5 ± 0.3 3.6E−7 ± 6.4E−8 0.55 ± 0.02 3.2E−5 ± 4.8E−8 1.7E−11 ± 2.1E−12 0.77 ± 0.01 PzIL8a 34.6 ± 1 6.7 ± 0.2 3.6E−7 ± 4.6E−8 0.46 ± 0.01 2.3E−5 ± 2.9E−8 4.8E−11 ± 3.2E−12 0.72 ± 0.01 PzIL9a 41.8 ± 0.5 6.1 ± 0.1 8.7E−7 ± 4.1E−8 0.51 ± 0.01 8.9E−6 ± 1.4E−8 6.6E−11 ± 2.9E−12 0.69 ± 0.01

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Acknowledgements

The authors thank the Scientific and Technical Research Council of Turkey (TUBİTAK, Grant KBAG-114Z740; COST Action CM 1206) for financial support.

Author contributions

H.A., A.D., and Ç.Ç. performed the experiments. Y.Y., and Z.Ç., contributed to sample preparation and charac-terization of the samples. A.K., analyzed the results, wrote the manuscript and drawn the figures. F.S. supervised the project. All authors discussed the results and commented on the manuscript.

competing interests

The authors declare no competing interests.

Additional information

Supplementary information is available for this paper at https ://doi.org/10.1038/s4159 8-020-68709 -5. Correspondence and requests for materials should be addressed to A.K. or F.S.

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