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1 Supporting Information for Syntheses, Structures and Properties of thenium Complexes of Tridentate Ligands: Isolation and Characterization of a Rare Example of thenium itrosyl Complex Containing {O} 5 Moiety Kaushik Ghosh*, Rajan Kumar, Sushil Kumar and Jay Singh Meena Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee Uttarakhand IDIA. ghoshfcy@iitr.ernet.in 1

2 Fig. S1 1 MR spectrum of complex 2 in CD 3 at room temperature. 2

3 41.97 Current Data Parameters AME RR-RULUPYP-31P EXPO 2 PROCO 1 F2 - Acquisition Parameters Date_ Time ISTRUM Spect PROBD 5 mm PABBO BB- PULPROG zgpg30 TD SOLVET CD3 S 126 DS 4 SW z FIDRES z AQ sec RG DW usec DE 6.00 usec TE K D sec d sec DELTA sec TD0 1 ======== CAEL f1 ======== UC1 31P P usec PL db SFO Mz ======== CAEL f2 ======== CPDPRG2 waltz16 UC2 1 PCPD usec PL db PL db PL db SFO Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 1.00 z GB 0 PC ppm Fig. S2 31 P MR spectrum of complex 2 in CD 3 at room temperature O Current Data Parameters AME RR-RULUPYO2-1 EXPO 1 PROCO 1 F2 - Acquisition Parameters Date_ Time ISTRUM Spect PROBD 5 mm PABBO BB- PULPROG zg30 TD SOLVET CD3 S 256 DS 2 SW z FIDRES z AQ sec RG 287 DW usec DE 6.00 usec TE K D sec TD0 1 ======== CAEL f1 ======== UC1 1 P usec PL db SFO Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 0.30 z GB 0 PC ppm Fig. S3 1 MR spectrum of complex 3 in CD 3 at room temperature. 3

4 39.19 Current Data Parameters AME RR-RULUPYO2-31P EXPO 2 PROCO 1 F2 - Acquisition Parameters Date_ Time ISTRUM Spect PROBD 5 mm PABBO BB- PULPROG zgpg30 TD SOLVET CD3 S 256 DS 4 SW z FIDRES z AQ sec RG DW usec DE 6.00 usec TE K D sec d sec DELTA sec TD0 1 ======== CAEL f1 ======== UC1 31P P usec PL db SFO Mz ======== CAEL f2 ======== CPDPRG2 waltz16 UC2 1 PCPD usec PL db PL db PL db SFO Mz F2 - Processing parameters SI SF Mz WDW EM SSB 0 LB 1.00 z GB 0 PC ppm Fig. S4 31 P MR spectrum of complex 3 in CD 3 at room temperature O O Fig. S5 1 MR spectrum of complex 1 in CD 3 at room temperature. 4

5 O 15 (O 4 ) Fig. S6 1 MR spectrum of complex 4 in CD 3 C at room temperature. Fig. S7 31 P MR spectrum of complex 4 in CD 3 at room temperature. 5

6 Table S1 1 MR Spectral Data [, ppm (J, z)] of Complexs 1, 2, 3, 4. Compd Other protons (ligand ) (, 15 and ligand ) (, 15 and ligand ) (, 15 and ligand ) Absorbance Wavelength (nm) Fig. S8 Electronic absorption spectra of 1 (red line) and 4 (black line) in acetonitrile solutions. 6

7 90 80 Transmittance cm cm Wavenumber (cm -1 ) Fig. S9 Infrared spectrum of complex 1. IR (KBr disk, cm 1 ): 1871 (ν O ) and 1654 (ν CO ) cm Transmittance cm cm cm Wavenumber (cm -1 ) Fig. S10 Infrared spectrum of complex 4. IR (KBr disk, cm 1 ): 1890 (ν O ), 1092, 623 (ν O4 ), 746, 694, 522 (ν PPh3 ) cm 1. 7

8 Absorbance nm Mb-O Oxidized Mb Reduced Mb Reduced Mb + 1 in dark Wavelength(nm) Fig. S11 Electronic spectra of conversion of reduced myoglobin to Mb O adduct upon reaction with 1 in buffer solution (50 mm phosphate buffer, p 6.8) under exposure of UV light. Green line, Met Mb (intense band at 409 nm); blue line, reduced Mb (near 433 nm, with excess of sodium dithionite); red dotted line, reduced Mb + solution of 1 (~ 4.5 x 10 5 M) in dark; black line, Mb O adduct for 1 at 422 nm when same solutions were exposed to UV light for 2-3 minutes Absorbance Wavelength (nm) Fig. S12 Reaction of photoreleased O derived from complex 1 with DPP radical (~ 10 5 M) in acetonitrile solution. 8

9 (a) % Transmittance (b) Wavenumber (cm -1 ) Absorbance Wavelength (nm) Fig. S13 (a) Infrared and (b) UV-Vis spectra (black line, complex 4; blue line, 4 (1 mm) + CA (8 mm); red line, 4 (1 mm) + CA (8 mm) + sodium dithionite (2 mm)) showing the conversion of {O} 6 to {O} 5 species when complex 4 was treated with ceric ammonium nitrate in acetonitrile solution. 9

10 Transmittance cm cm Wavenumber (cm -1 ) Fig. S14 Infrared spectrum of complex 5. IR (KBr disk, cm 1 ): 1910 (ν O ), 1391 (ν O3 ), 1085, 750, 695, 518 (ν PPh3 ) cm 1. 10

11 (a) calculated experimental Intensity Wavelength (nm) (b) calculated experimental Intensity Wavelength (nm) Fig. S15 Experimental and TDDFT calculated absorption spectra of (a) complex 1 and (b) complex 4. 11

12 Table S2 Selected bond distances (Å) and bond angles (º) for nitrosyl complexes 1 and 4 along with the optimized DFT bond parameters for comparison. Bond lengths (Å) Bond angles (deg.) Complex 1 X-ray DFT X-ray DFT (1) (1) (8) (1) (1) (4) (8) (1) (2) (8) (2) (1) (5) (10) (1) (2) 1.977(2) (1)(1) (2) (3) (1) (1) 2.074(2) (1) (1) (2) 79.12(9) (1) (4) 2.052(2) (4) (1) (2) 78.59(9) (1) (5) 1.761(2) (4) (1) (1) 88.88(7) (5) O(2) 1.147(3) (4) (1) (2) 90.14(7) O(2) (5) (1) 169.4(2) Complex 4 (1) (1) (12) (3) (1) (2) 77.71(15) (1) P(1) (13) (1) (1) (4) 96.44(16) (1) (4) 2.082(3) P(1) (1) (1) (5) (1) (3) 2.002(4) (4) (1) (3) 78.17(15) (1) (2) 2.077(3) (4) (1) (2) (14) (1) (1) 1.731(4) (2) (1) P(1) 92.53(9) (1) O(1) 1.142(4) (1) (1) P(1) 89.88(12) O(1) (1) (1) 173.7(4) Table S3 Calculated OMO compositions (in %) expressed in terms of individual fragments. Complex O Other [(L 1 )(O) 2 ] (1) [(L 2 )( )(O)] 2+ (4) [(L 2 )( )(O)] 3+ (5)

13 Table S4 Calculated TD-DFT excitation energies (in ev), oscillator strengths (f), and nature of transitions in the complexes 1 and 4.. Composition E (ev) Oscillator strength (f) Complex 1 λ theo (nm) λ exp (nm) OMO LUMO+2 (88%) OMO 1 LUMO+3 (6%) OMO LUMO+5 (49%) OMO 12 LUMO+1 (17%) OMO 1 LUMO+6 (4%) OMO 2 LUMO+2 (3%) OMO 10 LUMO+1 (3%) OMO 3 LUMO+2 (3%) OMO 12 LUMO (13%) OMO 3 LUMO+4 (13%) OMO 13 LUMO+1 (11%) OMO 14 LUMO+1 (10%) OMO 10 LUMO+1 (7%) OMO 9 LUMO+1 (5%) OMO 3 LUMO+5 (4%) OMO 13 LUMO (4%) OMO 14 LUMO (3%) OMO 10 LUMO+2 (53%) OMO 7 LUMO+4 (9%) OMO 11 LUMO+2 (7%) OMO 10 LUMO+3 (3%) OMO 7 LUMO+5 (3%) OMO 1 LUMO+7 (2%) OMO 5 LUMO+6 (2%)

Complex 4 OMO LUMO+2 (63%) OMO 2 LUMO+2 (3%) OMO 5 LUMO+2 (3%) OMO 4 LUMO+2 (5%) OMO 6 LUMO+2 (7%) OMO 11 LUMO (15%) 2.94 0.0355 420.

14 Complex 4 OMO LUMO+2 (63%) OMO 2 LUMO+2 (3%) OMO 5 LUMO+2 (3%) OMO 4 LUMO+2 (5%) OMO 6 LUMO+2 (7%) OMO 11 LUMO (15%) OMO 1 LUMO+6 (4%) OMO 1 LUMO+5 (3%) OMO 9 LUMO+4 (45%) OMO LUMO+6 (8%) OMO 10 LUMO+4 (24%) OMO 6 LUMO+5 (3%) OMO 12 LUMO+2 (2%) OMO 8 LUMO+4 (2%) Fig S16 Spin density distribution in complex 5. 14

15 + m/z = (M) + m/z = (M-) + Fig. S17 ESI-MS spectrum of complex 2 along with fragmentation pattern. 15

16 O 2 O 2 + m/z = (M) + m/z = (M-) + Fig. S18 ESI-MS spectrum of complex 3 along with fragmentation pattern. 16

17 O (O 3 ) 3 3 m/z = (M) + 2O 3, O 3 m/z = (M-3O 3 -O-) + O 3 L 2, O 3 O 2 (O 3 ), O 3 O 3 m/z = (M-L O 3 ) + m/z = (M-2O 3 ) + m/z = (M-3O 3 - ) + O, O, O (O 3 ) 2 (O3 ) m/z = (M--O- -3O 3 ) + m/z = (M-O-2O 3 ) + m/z = (M-O--2O 3 ) + Fig. S19 ESI-MS spectrum of complex 5 along with fragmentation pattern. 17

Spectroscopic Analysis of Flavonoid Quercetin from Methanol Extracts of Emblica Officinalis Fruits

Spectroscopic Analysis of Flavonoid Quercetin from Methanol Extracts of Emblica Officinalis Fruits Aditi Gupta Department of Chemistry, Govt. Degree College, Kathua, J&k, (India) ABSTRACT A brown coloured