Supporting Information. Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study

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1 Supporting Information Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study Ananya Baksi, 1 M. S. Bootharaju, 1 Pratap K. Chhotaray, 2 Papri Chakraborty, 1 Biswajit Mondal, 1 Shridevi Bhat, 1 Ramesh Gardas 2 and Thalappil Pradeep 1 * 1 DST Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras, Chennai , India. 2 Department of Chemistry, Institute of Technology Madras, Chennai , India. *Corresponding author, pradeep@iitm.ac.in Content: Serial Number Description Page Number S1 ITC of Ag 32 (SG) 19 (1 mm) vs. GSH (5 mm) at 303K S2 S2 ITC of Ag 32 (SG) 19 (1 mm) vs. GSH (7.5 mm) at 303K S3 S3 ITC of Ag 32 (SG) 19 (1 mm) vs. GSH (7.5 mm) at 313K S4 S4 ITC of Ag 32 (SG) 19 (1 mm) vs. GSH (7.5 mm) at 323K S5 S5 ITC of Ag 11 (SG) 7 (1 mm) vs. GSH (7.5 mm) at 323K S6 S6 TEM image of AgNP S7 S7 UV-Vis absorption spectra of the products from different S8 reaction S8 ITC of AgNP vs. GSH at 298K S9 S9 ph change while reaction S10 S10 Comparison between thermograph of O 2 purged and not purged S11 samples of Ag 32 (SG) 19 vs. GSH reaction. S11 Stability of Ag 11 (SG) 7 cluster in ascorbic acid medium S12 S12 ITC of Ag 11 (SG) 7 (1 mm) vs. GSH (7.5 mm) with O 2 purging S13 S13 Density vs. Temperature of different samples S14 S14 Speed of Sound vs. Temperature of different samples S15 S15 Isentropic compressibility vs. Temperature of different samples S16 S16 Coefficient of thermal expansion vs. Temperature of different S17 samples S17 Comparison among density, sound velocity, coefficient of thermal expansion and isentropic compressibility of different samples at 303K S18 S1

2 Supporting Information 1: µcal/sec B) kcal mol -1 of injectant A) Time (min) Molar Ratio C) D) Intensity N= 0.50 Sites k= M -1 H= cal/mol S= cal/deg.mol T= 303 K G= cal/mol Ag 32 (SG) 19 Reaction product Wavelength (nm) Figure S1. A) Real time isothermal titration calorimetric data of Ag 32 (SG) 19 (1 mm) vs. GSH (5 mm) (top) and B) respective heat change data (down) at 303 K. The thermodynamic parameters obtained are listed in C). Corresponding features were seen in UV-vis absorption as shown in D). S2

3 Supporting Information 2: µcal/sec Time (min) N= 0.50 Sites K= M -1 H= cal/mol S= cal/mol/deg T= 303 K G= cal/mol kcal mol -1 of injectant Molar Ratio Figure S2. A) Real time isothermal titration calorimetric data of Ag 32 (SG) 19 (1 mm) vs. GSH (7.5 mm) (top) and B) at 303 K respective heat change data (down). The thermodynamic parameters obtained are listed in C). S3

4 Supporting Information 3 kcal mol -1 of injectant µcal/sec Time (min) Molar Ratio N= 0.60 k= M -1 H= cal/mol S= cal/deg.mol T= 313 K G= cal/mol Figure S3. A) Real time isothermal titration calorimetric data of Ag 32 (SG) 19 (1 mm) vs. GSH (7.5 mm) (top) and B) at 313 K respective heat change data (down). The thermodynamic parameters obtained are listed in C). S4

5 Supporting Information 4: A) 0 µcal/sec B) kcal mol -1 of injectant Molar Ratio C) N= 0.60 Sites k= M -1 H= cal/mol S= cal/deg.mol T= 323 K G= cal/mol Figure S4. A) Real time isothermal titration calorimetric data of Ag 32 (SG) 19 (1 mm) vs. GSH (7.5 mm) (top) and B) at 323 K respective heat change data (down). The thermodynamic parameters obtained are listed in C). S5

6 Supporting Information 5: A) µcal/sec B) kcal mol -1 of injectant Time (min) Molar Ratio C) N 0.50 Sites K M -1 H E4 cal/mol S cal/deg.mol G cal/mol T 323 K Figure S5. A) Real time isothermal titration calorimetric data of Ag 11 (SG) 7 (1 mm) vs. GSH (7.5 mm) (top) and B) at 323 K respective heat change data (down). The thermodynamic parameters obtained are listed in C). S6

7 Supporting Information 6 A) 0.30 B) nm Absorbance nm Wavelength (nm) Figure S6. A) UV-vis absorption spectrum of AgNP protected with GSH showing the plasmon band at 407 nm characteristic of silver nanoparticles. B) TEM image of AgNP@SG showing 20 nm particles. A portion of the image is expanded. S7

8 Supporting Information Ag 32 (SG) 19 +GSH Ag 11 (SG) 7 +GSH AgNP+GSH Intensity Wavelength (nm) Figure S7. UV-vis absorption spectra of reaction product from different reactions showing similar products. S8

9 Supporting Information 8: A) C) Reaction Product B) Intensity Wavelength (nm) Figure S8. A) Real time isothermal titration calorimetric data of ( mm) vs. GSH (7.5 mm) (top) and B) at 298 K respective heat change data (down). The thermodynamic parameters obtained are listed in C). Corresponding change in the UV-vis absorption is shown in D). S9

10 Supporting Information 9: ph Concentration of GSH (mm) Figure S9: Change in ph with reaction when 1 mm of Ag 32 (SG) 18 cluster was reacted with 10 mm GSH solution. Equal volume of GSH was added at 10 minute interval. First data point is before the addition of GSH. Time was counted after adding GSH. We find that the solution becomes increasingly acidic in the course of the reaction. Free GSH contribution was ruled out by subtracting the contribution from GSH addition to pure water. The ph change observed in the reaction was measurable accurately. Experimental details are presented in the manuscript. S10

11 Supporting Information 10: 0 Kcal mol -1 of injectant With N 2 purging Without N 2 purging Molar Ratio Figure S10. Comparison of heat change for the reaction of Ag 32 (SG) 19 (1 mm) vs. GSH (10 mm) at 303 K with and without N 2 purging. S11

12 Supporting Information 11: Absorbance Cluster only 0 min 5 min 10 min 20 min 30 min 40 min 50 min 60 min 70 min 80 min Wavelength (nm) Figure S11: Cluster solution (in water) was taken in cuvette and 10 µl of 1 mm ascorbic acid solution (in water) and time dependent UV-vis spectra were measured. As the cluster was stable after 40 min,10 µl ascorbic solution at each 10 min time interval was added and continued measurement up to 80 min. S12

13 Supporting Information 12: 0 Kcal mol -1 of injectant -3-6 With O 2 purging Molar Ratio Figure S12. Comparison of heat change for the reaction of Ag 11 (SG) 7 (1 mm) vs. GSH (7.5 mm) at 303 K with O 2 purging. S13

14 Supporting Information 13: Ρ ρ (kg.m (Kgm -3 3 ) Water AgNO 3 Ag 11 (SG) 7 Ag 11 (SG) 7 +GSH Ag 32 (SG) 19 Ag 32 (SG) 19 + GSH AgNP AgNP+GSH Temperature (K) Figure S13. Temperature dependent change in density of various samples is showing decrease in density with increasing temperature. S14

15 Supporting Information 14: u (m/s) (ms -1 ) Water AgNO 3 Ag 11 (SG) 7 Ag 11 (SG) 7 +GSH Ag 32 (SG) 19 Ag 32 (SG) 19 + GSH AgNP AgNP+GSH Temperature (K) Figure S14. Temperature dependent change in sound velocity of various samples is showing increase in speed of sound with increasing temperature. S15

16 Supporting Information 15: Ρ ρ (kg.m (Kgm -3 3 ) Water AgNO 3 Ag 11 (SG) 7 Ag 11 (SG) 7 +GSH Ag 32 (SG) 19 Ag 32 (SG) 19 + GSH AgNP AgNP+GSH Temperature (K) Figure S15. Temperature dependent change isentropic compressibility of various samples is showing thiolates are more compressible than clusters or nanoparticles. S16

17 Supporting Information 16: α 10 4 (K 4 /K -1 ) AgNO 3 Ag 11 (SG) 7 Ag 11 (SG) 7 +GSH Ag 32 (SG) 19 Ag 32 (SG) 19 + GSH AgNP AgNP+GSH Temperature (K) Figure S16. Temperature dependent change in coefficient of thermal expansion of various samples is showing thiolates are more expandable than clusters or nanoparticles. S17

18 Supporting Information 17: A) C) ρ (kg/m 3 ) ρ (Kgm -3 ) Water AgNO 3 Ag 11 (SG) 7 Ag 32 (SG) 19 AgNP AgNO 3 +GSH Ag 11 (SG) 7 Ag 32 (SG) 19 +GSH +GSH α 10 4 (K -1 ) B) D) α 10 4 /K Water AgNO 3 Ag 11(SG) 7 Ag 32(SG) 19 AgNP AgNO 3 +GSH Ag 11(SG) 7 Ag 32(SG) 19 +GSH +GSH u (m/s) u (ms -1 ) βs (TPa (Tpa -1-1 ) ) Water AgNO 3 Ag 11(SG) 7 Ag 32(SG) 19 AgNP AgNO 3 +GSH Ag 11(SG) 7 Ag 32(SG) 19 +GSH +GSH Water AgNO 3 Ag 11 (SG) 7 Ag 32 (SG) 19 AgNP AgNO 3 +GSH Ag 11 (SG) 7 Ag 32(SG) 19 +GSH +GSH Figure S17. Comparative A) speed of sound, B) sound velocity, C) isothermal expansion and D) isentropic compressibility of different materials at 303K. S18