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1 . This journal is The Royal Society of Chemistry 2017 Electronic Supplementary Material (ESI) for Dalton Transactions Electronic Supplementary Information Real-time detection of oxalyl chloride based on a long-lived iridium(iii) probe Chun Wu, a Guodong Li, b Quan-Bin Han, c Ren-Jun Pei, d Jin-Biao Liu, ae * Dik-Lung Ma a * and Chung-Hang Leung b * a Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong, China. b State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macao, China. c School of Chinese Medicine, Hong Kong Baptist University, Kowloon Tong, Hong Kong, China. d CAS Key Laboratory for Nano-Bio Interface, Division of Nanobiomedicine, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, , China. e School of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou, China. * Corresponding authors. addresses: edmondma@hkbu.edu.hk (Dr. Dik-Lung Ma), duncanleung@umac.mo (Prof. Chung-Hang Leung) and liujbgood@hotmail.com (Dr. Jin Biao Liu). S1

2 TABLE OF CONTENTS Experimental details Table S1 Photophysical properties of complex 1 (10 μm). S3-S6 S6 Fig. S1 (a) 1 H NMR spectrum for complex 1 recorded in acetonitrile-d 3 ; (b) 13 C NMR spectrum for complex 1 recorded in acetonitrile-d 3 ; (c) HRMS spectrum for complex 1. S7 Fig. S2 (a) Emission spectra of complex 1 (10 μm) only, (COCl)₂ (40 μm) only, or a mixture of complex 1 (10 μm) and (COCl)₂ (40 μm) in DCM. (b) Absorption spectra of complex 1 (10 μm) with the presence and absence of (COCl)₂ (40 μm) in DCM. S8 Fig. S3 1 H NMR spectra for complex 1 (lower panel) and complex 1a (upper panel) recorded in acetonitrile-d 3. S8 Fig. S4 Excitation spectra and emission spectra of complex 1 (10 μm) in DCM with excitation wavelength at 330 nm. S9 Fig. S5 Emission spectra of complexes 1 14 (10 μm) in DCM with excitation wavelength at 330 nm. S9 Fig. S6 Emission spectra of complexes 1 (10 μm) towards (COCl)₂ (40 μm) in different solvent systems with the excitation wavelength at 330 nm. The inset shows the luminescence intensity enhancement upon addition of (COCl)₂. S9 Fig. S7 Graphical illustration for the detection procedure of (COCl)₂ with Color Grab (Loomatix) application installed on a smartphone (Samsung Galaxy Note 7) in the presence of UV light irradiation at 365 nm. S10 References S10 S2

3 Experimental Material Unless specified, all the reagents were purchased from Sigma Aldrich (St. Louis, MO) and used as received without further purification, and all aqueous solutions were prepared with Milli-Q water (18.2 MΩ cm -1 ) unless specified. Iridium chloride hydrate (IrCl 3 xh 2 O) was purchased from Precious Metals Online (Australia). General Experiment Mass spectrometry was performed in the Mass Spectroscopy Unit at Department of Chemistry, Hong Kong Baptist University, Hong Kong (China). Deuterated solvents for NMR purposes were obtained from Armar and used as received. 1 H and 13 C NMR were recorded on a Bruker Avance 400 spectrometer operating at 400 MHz ( 1 H) and 100 MHz ( 13 C). 1 H and 13 C chemical shifts were referenced internally to solvent shift (Acetonitrile-d3: 1 H, 1.94, 13 C, 1.32 and ). Chemical shifts are quoted in ppm, the downfield direction being defined as positive. Uncertainties in chemical shifts are typically ±0.01 ppm for 1 H and ±0.05 for 13 C. Coupling constants are typically ±0.1 Hz for 1 H- 1 H and ±0.5 Hz for 1 H- 13 C couplings. The following abbreviations are used for convenience in reporting the multiplicity of NMR resonances: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br, broad. All NMR data was acquired and processed using standard Bruker software (Topspin). Complex synthesis Complex 1 were prepared according to modified literature methods. 1,2, 3 Briefly, 2.1 equivalents of benzo[h]quinoline and 1 equivalent of IrCl 3 xh 2 O were mixed together S3

4 and further heated overnight at 120 C in 12 ml of 2-methoxyethanol/H 2 O (3/1). Afterwards, the mixture was filtered and washed by excessive deionized water and then diethyl ether for three times respectively to generate the dichloro-bridged dimer [Ir(F 2 phen) 2 Cl] 2. The oven-dried dimer was treated with 2.1 equivalents of 5,6- diamino-1,10-phenanthroline in dichloromethane (DCM) (4 ml) and methanol (4 ml) at ambient temperature for 10 h. Then, an excess of solid ammonium hexafluorophosphate (NH 4 PF 6 ) was added and the reaction was stirred for another 20 min. The brown powder thus obtained was isolated and filtrated by removing the solvent under reduced pressure, and the residue was purified by silica gel column chromatography employing DCM and methanol as solvent. Yield: 41%. Complex 1 1 H NMR (400 MHz, CD 3 CN) δ 8.57 (dd, J = 8.7, 1.1 Hz, 1H), 8.38 (dd, J = 8.1, 1.1 Hz, 1H), 8.06 (dd, J = 4.9, 1.1 Hz, 1H), 7.97 (d, J = 8.8 Hz, 1H), (m, 2H), (m, 2H), 7.58 (d, J = 7.6 Hz, 1H), 7.33 (dd, J = 8.1, 5.4 Hz, 1H), (m, 1H), 6.42 (d, J = 6.7 Hz, 1H), 4.76 (s, 2H). 13 C NMR (101 MHz, CD 3 CN) δ (m), (d, J = 26.5 Hz), (d, J = 19.9 Hz), (s), (m), (m), (s), (m), (d, J = 9.4 Hz), (s), (s), (s), (s), (s), (d, J = 12.1 Hz), (s). HRMS: Calcd. for C 38 H 26 N 6 IrPF 6 [M-PF 6 ] + : Found: Complex 2 Reported 4 Complex 3 Reported 5, 6 Complex 4 Reported 7 Complex 5 Reported 8 Complex 6 Reported 9 Complex 7 Reported 10 Complex 8 Reported 10 S4

5 Complex 9 Reported 6 Complex 10 Reported 11 Complex 11 Reported 6 Complex 12 Reported 7 Complex 13 Reported 7 Complex 14 Reported 7 Photophysical measurement Emission spectra and lifetime measurements for complex 1 were performed on a PTI TimeMaster C720 Spectrometer (Nitrogen laser: pulse output 335 nm) fitted with a 395 nm filter. Error limits were estimated: λ (±1 nm); τ (±10 %); φ (±10 %). All solvents used for the lifetime measurements were degassed using three cycles of freeze-vac-thaw. Luminescence quantum yields were determined using the method of Demas and Crosby with [Ru(bpy) 3 ][PF 6 ] 2 in degassed acetonitrile (ACN) as a standard reference solution (Φ r = 0.062) and were calculated according to the following reported equation (1): Φ s = Φ r (B r /B s )(n s /n r ) 2 (D s /D r ) (1) Where the subscripts s and r refer to the sample and reference standard solution respectively, n is the refractive index of the solvents, D is the integrated intensity, and Φ is the luminescence quantum yield. The quantity B was calculated by B = 1 10 AL, where A is the absorbance at excitation wavelength and L is the optical path length. (COCl)₂ detection. A stock solution of complex 1 (1 mm) was prepared in ACN for further use. The complex was diluted in DCM to a final concentration of 10 μm for 0.5 ml. After that, S5

6 2 μl of (COCl)₂ solution (10 mm) was added to the cuvette and the resulting spectra were recorded at 25 C on a PTI QM-1 spectrofluorometer (Photo Technology International, Birmingham, NJ). A double-beam spectrophotometer (Cary UV-300) was used for recording UV-Vis absorption spectra and a 400 MHz Bruker spectrometer was used for recording NMR spectra. For smartphone detection, the samples were prepared in eppendorf tubes (0.5 ml) instead of cuvettes following similar methods as above. The samples were exposed to UV light at 365 nm, and the pre-installed application Color Grab (Loomatix) was used to measure specific RGB values with a 12-megapixel rear-facing camera from a smartphone (Samsung Galaxy Note 7). Generated RGB values were futher analyzed based on the Red/Blue and Green/Blue channel intensity ratio to obtain the three-dimensional diagram. Table S1 Photophysical properties of complex 1 (25 μm). Complex Quantum λ ex / λ em / nm Lifetime / yield nm μs UV-Vis absorption λ abs / nm (ε / dm 3 mol -1 cm -1 ) 217 ( ), 268 ( ) S6

7 (a) (b) (c) S7

8 Fig. S1 (a) 1 H NMR spectrum for complex 1 recorded in acetonitrile-d 3 ; (b) 13 C NMR spectrum for complex 1 recorded in acetonitrile-d 3 ; (c) HRMS spectrum for complex 1. (a) (b) Fig. S2 (a) Emission spectra of complex 1 (10 μm) only, (COCl)₂ (40 μm) only, or a mixture of complex 1 (10 μm) and (COCl)₂ (40 μm) in DCM. (b) Absorption spectra of complex 1 (10 μm) with the presence and absence of (COCl)₂ (40 μm) in DCM. 1a 1 S8

9 Fig. S3 1 H NMR spectra for complex 1 (lower panel) and complex 1a (upper panel) recorded in acetonitrile-d 3. Fig. S4 Excitation spectra and emission spectra of complex 1 (10 μm) in DCM with excitation wavelength at 330 nm. Fig. S5 Emission spectra of complexes 1 14 (10 μm) in DCM with excitation wavelength at 330 nm. S9

10 Fig. S6 Emission spectra of complexes 1 (10 μm) towards (COCl)₂ (40 μm) in different solvent systems with the excitation wavelength at 330 nm. The inset shows the corresponding luminescence intensity enhancement upon addition of (COCl)₂. Fig. S7 Graphical illustration for the detection procedure of (COCl)₂ with Color Grab (Loomatix) application installed on a smartphone (Samsung Galaxy Note 7) in the presence of UV light irradiation at 365 nm. References 1. M. Wang, Z. Mao, T. S. Kang, C. Y. Wong, J. L. Mergny, C. H. Leung, D. L. Ma, Chem. Sci., 2016, 7, D.-L. Ma, T. Xu, D. S.-H. Chan, B. Y.-W. Man, C.-H. Leung, Nucleic Acids Res., 2011, 39, e W. Zhang, F. Zhang, Y.-L. Wang, B. Song, R. Zhang and J. Yuan, Inorg. Chem., 2017, 56, H.-J. Zhong, L. Lu, K.-H. Leung, C. C. Wong, C. Peng, S.-C. Yan, D.-L. Ma, Z. Cai, H.-M. D. Wang and C.-H. Leung, Chem. Sci., 2015, 6, L.-J. Liu, L. Lu, H.-J. Zhong, B. He, D. W. J. Kwong, D.-L. Ma and C.-H. Leung, J. Med. Chem., 2015, 58, L. Lu, H.-J. Zhong, S.-L. H. Modi Wang, H.-W. Li, C.-H. Leung and D.-L. Ma, Sci. Rep., 2015, 5, D. L. Ma, L. J. Liu, K. H. Leung, Y. T. Chen, H. J. Zhong, D. S. H. Chan, H. M. D. Wang and C. H. Leung, Angew. Chem. Int. Ed. Engl., 2014, 53, M. Wang, K.-H. Leung, S. Lin, D. S.-H. Chan, C.-H. Leung and D.-L. Ma, J. Mate. Chem. B, 2014, 2, K.-H. Leung, L. Lu, M. Wang, T.-Y. Mak, D. S.-H. Chan, F.-K. Tang, C.-H. Leung, H.-Y. Kwan, Z. Yu and D.-L. Ma, PloS One, 2013, 8, e S10

11 10. L. Lu, D. S.-H. Chan, D. W. Kwong, H.-Z. He, C.-H. Leung and D.-L. Ma, Chem. Sci., 2014, 5, L. Lu, M. Wang, L.-J. Liu, C.-H. Leung and D.-L. Ma, ACS Appl. Mater. Interfaces, 2015, 7, S11