Phenanthroline Based Ruthenium Complexes for Enhanced Charge Transportation in Solvent-Free

Phenanthroline based Ruthenium Complexes for Enhanced Charge Transportation in Solvent-free Ionic Liquid Electrolyte

Jonnalagadda Gopinatha, Kyung Hee Parkb, Seok-Jae Kimb, Vundadi Santosha, Annadanam V. Sesha Sainatha,*, Marshal Dhayalc,**

aPolymers and Functional Materials Division and Academy of Scientific & Innovative Research (AcSIR), CSIR-Indian Institute of Chemical Technology, Uppal Road, Hyderabad 500007, India

bDepartment of Dental Materials, Chonnam National University, Gwangju 61186, Republic of Korea

cInnovation Cell and Clinical Research Facility, Medical Biotechnology Complex, CSIR- Centre for Cellular and Molecular Biology, Uppal Road, Hyderabad- 500007, India

*Corresponding author. Tel: +91-40-27193149; Fax: +91-40-27193991; E-mail address: (A. V. S. Sainath).

**Corresponding author. Tel: +91-271-92500; Fax: +91-40- 271-60591; E-mail address: (M. Dhayal).

Contents

1. The 1,10-phenantroline based ruthenium metal complexes synthesis and characterization

Figure S1. NMR spectra of the 1,10-phenanthroline based ruthenium complexes (A, B and C) 1H and (Aˈ, Bˈ and Cˈ) 13C.

Figure S2.Cyclic voltammetry response of the PRC1with various scan rate (mV/s) [DMF, 2.5 mM].

Figure S3. Cyclic voltammetry response of the PRC2 with various scan rate (mV/s) [DMF, 2.5 mM].

Figure S4. Cyclic voltammetry response of the PRC3 with various scan rate (mV/s) [DMF, 2.5 mM].

Figure S5. Impedance measurements of the PRCs with 1 wt.% as an additive in IL electrolyte and neat IL at dark condition.

Figure S6. At dark condition measurements of the PRC2 with 0.1, 1 and 3 wt. % additive in IL and neat IL electrolyte (a) Nyquist plot of impedance, (b) Bode plot of impedance and (c) phase shift in Bode plot.

1. The 1,10-phenantroline based ruthenium metal complexes synthesis and characterization

1.1. Synthesis of tris[1,10-phenanthroline]ruthenium(II) hexaflouro phosphate (PRC1) The PRC1 was synthesized as reported earlier [1]. Yield: 90%. ESI–MS: m/z: 780 [M+H]+.

1.2. Synthesis of PRC2 and PRC3 intermediates

1.2.1. Synthesis of 3-bromo-1,10-phenanthroline

The bromination of 1,10-phenanthrolinewasprepared as reported earlier [2]. Mp: 169-170 °C. 1H NMR (300 MHz, CDCl3, δ): 9.20 (dd, J=4.4, 1.5 Hz, 1H), 9.19 (d, J=2.2 Hz, 1H), 8.40 (d, J=2.2Hz, 1H), 8.26 (dd, J=8.1Hz, 1.5Hz, 1H), 7.83 (d, J=8.8Hz, 1H), 7.72 (d, J=8.8Hz, 1H) and 7.65 (dd, J=8.1, 4.4 Hz, 1H). ESI–MS: m/z: 259 [M+H]+.IR (KBr, cm-1, ν): 3021 (C-H), 1948, 1885 and 1855 (aromatic skeletal vibrations),1577 (C=C, Ar), 1416 (–C=N) and 896 and 833 (C–Br).

1.2.2. Synthesis of tributyl(prop-1-en-2-yl)stannane

The organotin compound was prepared as cited in literature [3].1H NMR (500 MHz, CDCl3, δ): 5.697 (s, 1H), 5.07 (s, 1H), 1.972 (m, 3H), 1.56-1.288 (m, 12H), 0.934 (m, 6H) and 0.877 (m, 9H). 13C NMR (101 MHz, CDCl3, δ): 150.2, 125.4, 29, 27.3, 13.5 and 9.0. ESI–MS: m/z: 333 [M+H]+.

1.2.3. Synthesis of 3-(prop-1-en-2-yl)-1,10-phenanthroline (P-Phen)

The 3-bromo 1,10-phenathroline (5g, 27mmol), tetrakis(triphenylphosphine)palladium(0) (0.96 mmol), copper iodide (0.96mmol), cesium fluoride (38.6mmol) and tributyl(prop-1-en-2-yl)stannane (27.7mmol) were dissolved in 100 mL dry DMF and freeze-pump-thaw cycle was performed for two times [4]. The reaction mixture was stirred for 12 h at 90 °C. After completion of the reaction, the reaction mixture is passes through celite and extracted with DCM, then washed with brine solution and finally with water. The product was purified by column chromatography with 2% methanol in DCM. 1H NMR (300 MHz, CDCl3, δ): 9.341 (d, J=2.28Hz, 1H), 9.177 (m, 1H), 8.193 (d, J=2.28Hz, 1H), 7.98 (m, 1H), 7.625 (m, 2H), 7.48-7.44 (m, 1H), 5.67 (s, 1H), 5.34 (s, 1H) and 2.31 (s, 3H). 13C NMR (101 MHz, CDCl3, δ): 149.9, 147.743, 145.69, 144.67, 139.8, 135.53, 132.411, 131.67, 128.13, 126.25, 122.44, 114.87 and 21.22. ESI–MS: m/z: 221 [M+H]+.IR (KBr, cm-1, ν): 3051 (Ar C-H), 2972, 2870 (methyl C-H) and1630 (C=C).

1.2.4. Synthesis of bis(1,10-phenanthrolin)ruthenium(II) chloride [Ru(phen)2Cl2]

The RuCl3.xH2O (0.3 g, 1.44mmol), Phen (0.52 g, 2.892mmol), LiCl (0.004075 g, 0.097mmol) and dry DMF (10 mL) were refluxed for 8 h[1]. After that, the reaction mixture was cooled to room temperature and added acetone. The resultant solution was kept at 0 °C for an overnight. Then, yielded dark green black crystals were filtered. The crystals were washed three times with 100 ml of water followed by diethyl ether and subsequently dried under vacuum.

Figure S1. NMR spectra of the 1,10-phenanthroline based ruthenium complexes (A, B and C) 1H and (Aˈ, Bˈ and Cˈ) 13C.

Figure S2. Cyclic voltammetry response of the PRC1 with various scan rate (mV/s) [DMF, 2.5 mM].

Figure S3. Cyclic voltammetry response of the PRC2 with various scan rate (mV/s) [DMF, 2.5 mM].

Figure S4. Cyclic voltammetry response of the PRC3 with various scan rate (mV/s) [DMF, 2.5 mM].

Figure S5. Impedance measurements of the PRCs with 1 wt.% as an additive in IL electrolyte and neat IL at dark condition.

Figure S6. At dark condition measurements of the PRC2 with 0.1, 1 and 3 wt.% additive in IL and neat IL electrolyte (a) Nyquist plot of impedance, (b) Bode plot of impedance and (c) phase shift in Bode plot.

References

[1] Bhuiyan AA, Kudo S, Bartlett J (2010) Synthesis and characterization of ruthenium complexes containing chlorophenanthroline and bipyridine. J Ark AcadSci 64:33-40.

[2] Tzalis D, Tor Y, Failla S, Siegel JS (1995) Simple One-Step Synthesis of 3-Bromo and 3,8-Dibromo- 1,10-Phenanthroline: Fundamental Building Blocks in the Design of Metal Chelates. Tetrahedron Lett. 36:3489-3490.

[3] Langle SL, Abarbri M, Thibonnet J, Duchêne A (2009) Stille Coupling Made Easier-The Synergic Effect of Copper(i) Salts and the Fluoride Ion. J. Organomet. Chem. 694:2368-2374.

[4] Simon PHM, Lee V, Baldwin JE (2004) Stille Coupling made easier—The synergic effect of copper(I) salts and the fluoride ion. Angew. Chem. Int. Ed. 43:1132-1135.

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