Table of Contents:

Optical Spectra of products SI-2

Lifetimes Spectra SI-3

Table of lifetime values SI-3

Table of NMR integral values SI-4

Calculation of dye loading SI-4

Expanded view of square wave voltammograms SI-5

Representative EDS images SI-6

General Procedure SI-7

Instrumentation SI-7

Individual Experimental Procedures and Characterization DataSI-8 – SI-12

1H NMR and 13C NMR SpectraSI-13 – SI-22

FIG S1. Comparison of the absorption spectra and emission spectra of the i- and bi- systems before and after ligand exchange. (a) and (b) are the UV-Vis spectra (c) and (d) are the emission spectra of i-and bi- Au25 before and after ligand exchange and (e) and (f) are the emission spectra of the same in the near-IR region.

FIG. S2. Lifetime measurement of (a) the i- and (b) bi- Au25 before and after exchange reaction.

Table S1. Lifetime data of the labeled and unlabeled products.

Sample

tau[1] (ns)

tau[2] (ns)

a[1]

a[2]

Chi2

i-Au25

7.02E-001 ± 4.86E-001

6.79E-001 ± 3.60 E-001

1.16E-002 ± 7.04E-003 (4.11E+001 ± 2.48E+001%)

1.66E-002 ± 7.17E-003 (5.88E+001 ± 2.53E+001%)

1.48E+000

i- Au25LE

1.97E-002 ± 6.21E-001

3.023E-001 ± 1.44E-003

-2.88E-001 ± 2.490E-003 (-7.47E+001 ± 6.48E-001%)

3.85E-001 ± 1.28E-003 (1.00E+002 ± 3.34E-001%)

3.43E+000

bi-Au25LE

1.62E-001 ± 3.94E-002

1.63E-001 ± 4.18E-002

5.52E-001 ± 6.67E-002 (5.23E+001 ± 6.32E+000%)

5.036E-001 ± 6.59E-002 (4.76E+001 ± 6.24E+000%)

1.17E+000

Cou-SH

1.366E-002 ± 3.42E+001

7.34E-001 ± 6.99E-003 (1.00E+002 ± 9.52E-001%)

1.47E+000

Table S2. Comparing the integral values form ROI selected in the proton-NMR spectra of i- and bi- Au25LE.

i-Au25LE

Area

Area per Proton

Ligand ratio

Hexanethiol

2.47E-03

1.24E-03

15.9

Cou-SH

2.33E-04

7.77E-05

1.0

Bi-Au25LE

Area

Area per Proton

Ligand ratio

Hexanethiol

2.81E-03

1.41E-03

1.0

Cou-SH

5.12E-03

1.71E-03

1.2

Triphenylphosphine

6.03E-02

1.00E-02

7.1

Calculation for dye loading from UV spectra.

The concentration of the dye is then calculated using the calculated absorbance, extinction coefficient of the dye at 320 nm, and Beer’s law.

The number of moles of the coumarin dye was calculated based on the concentration.

The number of molecules of the coumarin dye was calculated with Avogadro’s number.

Beer’s law was used to determine the concentration of the gold hexanethiol product with the extinction coefficient and absorbance measured at 680 nm.

The number of moles and molecules of the gold particles were calculated based on the concentration. The ratio of gold clusters to dye was calculated.

FIG. S3. Comparison of the (zoomed in) forward and backward scans of the oxidation potentials from the square wave voltammograms of the i-Au25 (a) and (b) and bi-Au25 (c) and (d) before and after exchange.

FIG. S4. EDS Analysis of (a) i-Au25 and (b) bi-Au25.

Synthesis of coumarin thiol ligand:

General procedures and materials. All reactions were carried out under an atmosphere of argon with magnetic stirring unless otherwise indicated. ACS reagent grade acetone, diethyl ether (Et2O), ethyl acetate (EtOAc), hexanes, methanol (CH3OH), tetrahydrofuran (THF) and toluene (PhCH3) were purchased from Fisher Scientific and used without further purification. Yields refer to isolated material that was found to be chromatographically and spectroscopically homogeneous. Reactions were monitored by thin layer chromatography (TLC) using glass plates pre-coated with a 0.25 mm layer of silica gel containing a fluorescent indicator. TLC plates were visualized by exposure to ultraviolet light and subsequently stained with acidic ethanolic para-anisaldehyde solution followed by heating on a laboratory hot plate. Silica gel for flash column chromatography was purchased from Sigma–Aldrich (catalog # 717185, 60 Å pore size, 40–63 μm particle size, 230–400 mesh).

Instrumentation. Proton nuclear magnetic resonance (1H NMR) spectra were obtained on a JEOL 400 SS spectrometer at 400 MHz and were calibrated to the residual monoprotio solvent peak (chloroform: 7.26 ppm). Coupling constants were extracted assuming first-order coupling, and peak multiplicities are abbreviated as follows: s = singlet, d = doublet, t = triplet, q = quartet, quint = quintet, m = multiplet, br = broad signal, and app = apparent signal. Each discrete signal is reported as follows: chemical shift in parts per million (integration, multiplicity, coupling constant).

Carbon nuclear magnetic resonance (13C NMR) spectra were obtained on the same instrument at 100 MHz and calibrated to the deuterated solvent peak (chloroform: 77.1 ppm). Each discrete signal is reported as follows: chemical shift in parts per million (multiplicity, coupling constant).

Infrared (IR) spectra were recorded on a Thermo Scientific Nicolet iS10 spectrometer using an ATR accessory. High resolution mass spectrometry (HRMS) was carried out using a Kratos MS 50 with electrospray ionization (ESI). Melting points were determined using a Digimelt SRS digital melting point apparatus and are uncorrected.

To a flame-dried 500 mL flask under argon equipped with a magnetic stirring bar was added a solution of methyl acetoacetate (10.0 mL, 92.7 mmol, 1.00 eq.) in 250 mL of THF. This solution was cooled to 0 °C in an ice bath, and solid sodium hydride (60% dispersion in mineral oil, 3.71 g, 92.7 mmol, 1.00 eq.) was added in 500 mg portions over the course of five minutes. Vigorous gas evolution was observed, and the reaction mixture was stirred at 0 °C for an additional 10 minutes after gas evolution ceased. A 2.5 M solution of n-butyllithium in hexanes (37.1 mL, 92.7 mmol, 1.00 eq.) was then added dropwise over the course of 10 minutes. After addition was complete, the resulting bright yellow dianion solution was stirred at 0 °C for an additional 10 minutes before cooling to -50 °C in a dry ice / acetone bath. A solution of freshly distilled 1,5-dibromopentane (21.3 g, 92.7 mmol, 1.00 eq.) in 50 mL of THF was added to the reaction mixture dropwise over 15 minutes, and stirring was continued at -50 °C for three hours before the reaction mixture was removed from the cooling bath and allowed to warm slowly to room temperature. After 2.5 hours, TLC (3:1 hexanes / EtOAc, UV / anisaldehyde) showed partial conversion of methyl acetoacetate (Rf = 0.26, stains pink/red) to the product of (Rf = 0.34, stains purple). The reaction was quenched by the careful addition of saturated aqueous NH4Cl solution and diluted with water and Et2O. The layers were separated, and the organic phase was dried over anhydrous Na2SO4. The solvent was removed under reduced pressure to give an orange oil that was purified by column chromatography (4:1 hexanes / EtOAc) to give β-keto ester 1 (6.28 g, 26%) as a yellow oil.

1H NMR (400 MHz, CDCl3): δ 3.73 (3H, s), 3.44 (2H, s), 3.40 (2H, t, J = 6.8 Hz), 2.54 (2H, t, J = 7.3 Hz), 1.85 (2H, app quint, J = 7.1 Hz), 1.61 (2H, app quint, J = 7.3 Hz), 1.48–1.40 (2H, m), 1.36–1.28 (2H, m).

13C NMR (100 MHz, CDCl3): δ 202.7, 167.7, 52.4, 49.1, 42.9, 33.9, 32.5, 28.1, 27.9, 23.2.

HRMS (ESI–TOF):

Calculated [M+H+]: 265.04393 for [C10H17BrO3 + H+]

Observed [M+H+]: 265.04331

Error: –2.3 ppm

IR (thin film): νmax = 2935, 2858, 1744, 1713, 1628, 1436, 1239, 1008, 644 cm-1.

To a flame-dried 250 mL flask under argon equipped with a magnetic stirring bar was added a solution of β-keto ester 1 (5.00 g, 18.9 mmol, 1.10 eq.) in 200 mL of PhCH3. Solid resorcinol (1.89 g, 17.1 mmol, 1.00 eq.) was added followed by solid para-toluenesulonic acid monohydrate (326 mg, 1.71 mmol, 0.10 eq.). The flask was equipped with a Dean–Stark trap and a water-cooled condenser, and the reaction mixture was heated to reflux. The reaction mixture gradually darkened from light yellow to orange to red, and the reaction was heated at reflux for 18 hours. After this time, TLC (1:1 hexanes / EtOAc, UV / anisaldehyde) showed complete consumption of β-keto ester 1 (Rf = 0.59, stains purple), a small amount of unreacted resorcinol (Rf = 0.34, stains bright red), and formation of the product (Rf = 0.37, strongly UV-active; does not stain). The reaction mixture was allowed to cool to room temperature and was diluted with water and EtOAc. The layers were separated, and the organic phase was dried over anhydrous Na2SO4. The solvent was removed under reduced pressure to give a dark red solid that was adsorbed onto 50 g of silica and purified by column chromatography (2:1 hexanes / EtOAc) to afford hydroxycoumarin 2 (4.66 g, 83%) as an off-white solid (m.p. 109.1‒111.9 °C).

1H NMR (400 MHz, CDCl3): δ 8.69 (1H, s), 7.52 (1H, d, J = 8.8 Hz), 7.07 (1H, d, J = 2.3 Hz), 6.92 (1H, dd, J = 8.8 Hz, 2.3 Hz), 6.13 (1H, s), 3.40 (2H, t, J = 6.7 Hz), 2.74 (2H, t, J = 7.3 Hz), 1.86 (2H, app quint, J = 7.1 Hz), 1.70 (2H, app quint, J = 7.1 Hz), 1.53–1.40 (4H, m).

13C NMR (100 MHz, CDCl3): δ 163.3, 160.5, 158.3, 155.2, 125.8, 113.9, 112.5, 109.8, 103.6, 33.9, 32.6, 31.9, 28.6, 28.2, 27.9.

HRMS (ESI–TOF):

Calculated [M+H+]: 325.04393 for [C15H17BrO3 + H+]

Observed [M+H+]: 325.04329

Error: –2.0 ppm

IR (thin film): νmax = 3476, 3091, 2929, 2854, 1692, 1660, 1618, 1604, 1565, 1354, 1144, 886, 645 cm-1.

To a flame-dried 250 mL flask under argon equipped with a magnetic stirring bar was added a solution of hydroxycoumarin 2 (3.73 g, 11.5 mmol, 1.00 eq.) in 100 mL of acetone. Neat iodomethane (1.78 mL, 28.6 mmol, 2.50 eq.) was added followed by solid anhydrous potassium carbonate (7.92 g, 57.3 mmol, 5.00 eq.), and the resulting suspension was stirred vigorously at room temperature for 18 hours. After this time, TLC (1:1 hexanes / EtOAc, UV / anisaldehyde) showed complete consumption of hydroxycoumarin 2 (Rf = 0.37) and clean formation of the product (Rf = 0.63, stains faintly white). The reaction mixture was diluted with water and EtOAc, and the layers were separated. The aqueous phase was extracted with one additional portion of EtOAc, and the combined organic layers were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude solid was purified by column chromatography (2:1 hexanes / EtOAc) to give methoxycoumarin 3 (3.57 g, 92%) as a white solid (m.p. 70.9‒72.2 °C).

1H NMR (400 MHz, CDCl3): δ 7.51 (1H, d, J = 8.8 Hz), 6.85 (1H, dd, J = 8.8 Hz, 2.5 Hz), 6.81 (1H, d, J = 2.5 Hz), 6.11 (1H, s), 3.86 (3H, s), 3.19 (2H, t, J = 6.9 Hz), 2.72 (2H, t, J = 7.2 Hz), 1.83 (2H, app quint, J = 6.8 Hz), 1.69 (2H, app quint, J = 7.1 Hz), 1.50–1.41 (4H, m).

13C NMR (100 MHz, CDCl3): δ 162.6, 161.5, 156.3, 155.6, 125.3, 112.9, 112.4, 110.9, 101.1, 55.8, 33.3, 31.8, 30.2, 28.4, 28.1, 7.0.

HRMS (ESI–TOF):

Calculated [M+H+]: 339.05958 for [C16H19BrO3 + H+]

Observed [M+H+]: 339.05928

Error: –0.9 ppm

IR (thin film): νmax = 3072, 2926, 2843, 1732, 1614, 1289, 1276, 1137, 1023, 993, 977, 881, 839, 632 cm-1.

To a flame-dried 200 mL flask under argon equipped with a magnetic stirring bar was added a solution of methoxycoumarin 3 (2.80 g, 8.24 mmol, 1.00 eq.) in 100 mL of acetone. Solid potassium thioacetate (1.04 g, 9.06 mmol, 1.10 eq.) was added in a single portion, and the reaction mixture was stirred at room temperature for 45 minutes. After this time, TLC (3:1 hexanes / EtOAc, UV /anisaldehyde) showed complete consumption of methoxycoumarin 3 (Rf = 0.29) and clean formation of the product (Rf = 0.22, stains bright yellow). The reaction mixture was diluted with water and EtOAc, and the layers were separated. The aqueous phase was extracted with one additional portion of EtOAc, and the combined organic layers were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude solid was purified by column chromatography (4:1 hexanes / EtOAc) to give thioester 4 (2.62 g, 95%) as a white solid (m.p. 77.6‒78.5 °C).

1H NMR (400 MHz, CDCl3): δ 7.50 (1H, d, J = 8.8 Hz), 6.84 (1H, dd, J = 8.8 Hz, 2.6 Hz), 6.81 (1H, d, J = 2.5 Hz), 6.10 (1H, s), 3.86 (2H, s), 2.85 (2H, t, J = 7.3 Hz), 2.70 (2H, t, J = 7.1 Hz), 2.31 (3H, s), 1.67 (2H, app quint, J = 6.9 Hz), 1.58 (2H, app quint, J = 7.0 Hz), 1.47–1.37 (4H, m).

13C NMR (100 MHz, CDCl3): δ 196.0, 162.6, 161.5, 156.4, 155.6, 125.3, 112.9, 112.4, 110.9, 101.1, 55.8, 31.8, 30.7, 29.4, 29.00, 28.95, 28.5, 28.1.

HRMS (ESI–TOF):

Calculated [M+H+]: 335.13170 for [C18H22O4S + H+]

Observed [M+H+]: 335.13128

Error: –1.3 ppm

IR (thin film): νmax = 3075, 2937, 2890, 1712, 1689, 1608, 1276, 1138, 977, 854, 634 cm-1.

To a flame-dried 100 mL flask under argon equipped with a magnetic stirring bar was added a solution thioester 4 (887 mg, 2.65 mmol, 1.00 eq.) in 45 mL of CH3OH. Solid anhydrous potassium carbonate (1.83 g, 13.2 mmol, 5.00 eq.) was added in a single portion, and the resulting suspension was stirred vigorously at room temperature for one hour. After this time, TLC (double elution in 3:1 hexanes / EtOAc, UV / anisaldehyde) showed complete consumption of thioester 4 (Rf = 0.47) and clean formation of the product (Rf = 0.51). The reaction mixture was carefully acidified to pH 2 with 3 M aqueous HCl solution and diluted with EtOAc. The layers were separated, and the aqueous phase was extracted with one additional portion of EtOAc before the combined organic phases were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude solid was purified by column chromatography (2:1 hexanes / EtOAc) to afford thiol 5 (689 mg, 89%) as a white solid (m.p. 102.7‒103.9 °C).

1H NMR (400 MHz, CDCl3): δ 7.51 (1H, d, J = 8.8 Hz), 6.85 (1H, dd, J = 8.8 Hz, 2.6 Hz), 6.81 (1H, d, J = 2.5 Hz), 6.11 (1H, s), 3.86 (3H, s), 2.71 (2H, t, J = 7.2 Hz), 2.53 (2H, app q, J = 7.3 Hz), 1.72–1.66 (2H, m), 1.65–1.59 (2H, m), 1.49–1.39 (4H, m), 1.33 (1H, t, J = 7.4 Hz, –SH).

13C NMR (100 MHz, CDCl3): δ 162.6, 161.6, 156.4, 155.6, 125.3, 112.9, 112.4, 110.9, 101.1, 55.8, 33.8, 31.8, 29.0, 28.2, 28.1, 24.6.

HRMS (ESI–TOF):

Calculated [M+H+]: 293.12114 for [C16H20O3S + H+]

Observed [M+H+]: 393.12067

Error: –1.6 ppm

SUPPORTING INFORMATION FOR

Variations in electronic states of coumarin hexanethiolate labeled i-Au25 and bi-Au25 clusters

1Angela Meola, 1Nicole Hondrogiannis, 1Pierce Brown, 2Maksym Zhukovskyi, 3Zheng Zheng, 3Zeev Rosenzweig, 1Keith Reber, 1Mary Sajini Devadas*

1Department of Chemistry, Towson University, Towson, MD

2Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN

3Department of Chemistry and Biochemistry, University of Maryland Baltimore County, Baltimore, MD

*Corresponding author email: mdevadas@towson.edu

IR (thin film): νmax = 3096, 3070, 2931, 2858, 2553, 1706, 1611, 1557, 1287, 1146, 867, 732, 705 cm-1.

SI-8

1

1H NMR

(400 MHz, CDCl3)

SI-2

(500 MHz, CDCl3)

SI-2

(125 MHz, CDCl3)

1

13C NMR

(100 MHz, CDCl3)

2

1H NMR

(400 MHz, CDCl3)

2

13C NMR

(100 MHz, CDCl3)

3

1H NMR

(400 MHz, CDCl3)

3

13C NMR

(100 MHz, CDCl3)

4

1H NMR

(400 MHz, CDCl3)

4

13C NMR

(100 MHz, CDCl3)

5

1H NMR

(400 MHz, CDCl3)

5

13C NMR

(100 MHz, CDCl3)

SI-22

H

3

COCH

3

OO

OCH

3

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Br

1) NaH, n-BuLi, THF, 0 °C

2)

BrBr

-50 °C to rt; then aq. NH

4

Cl

26%

1

OCH

3

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Br

1

OHHO

p-TsOH, PhCH

3

reflux (DeanStark), 83%

OHOO

Br

2

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Br

2

OH

3

COO

Br

3

CH

3

I, K

2

CO

3

acetone, rt, 92%

OH

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S

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acetone, rt, 95%

CH

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3

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Br

OCH

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.

3

9

1

1

2

.

8

5

1

2

5

.

3

1

1

5

5

.

6

3

1

5

6

.

2

8

1

6

1

.

5

0

1

6

2

.

5

8

OH

3

COO

SCH

3

O

OH

3

COO

SCH

3

O

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

f1 (ppm)

4

.

1

5

2

.

0

2

2

.

1

7

2

.

9

6

2

.

0

4

2

.

0

1

3

.

0

4

0

.

9

8

0

.

9

8

0

.

9

9

1

.

0

0

1

.

4

0

1

.

4

1

1

.

4

2

1

.

4

3

1

.

4

3

1

.

5

4

1

.

5

6

1

.

5

7

1

.

5

9

1

.

6

1

1

.

6

3

1

.

6

5

1

.

6

7

1

.

6

9

1

.

7

1

2

.

3

1

2

.

6

8

2

.

7

0

2

.

7

2

2

.

8

4

2

.

8

5

2

.

8

7

3

.

8

6

6

.

1

0

6

.

8

0

6

.

8

1

6

.

8

3

6

.

8

4

6

.

8

5

6

.

8

6

7

.

2

6

7

.

4

9

7

.

5

1

0102030405060708090100110120130140150160170180190200210

f1 (ppm)

2

8

.

1

3

2

8

.

4

9

2

8

.

9

5

2

9

.

0

0

2

9

.

4

3

3

0

.

7

0

3

1

.

8

0

5

5

.

7

9

7

6

.

7

8

7

7

.

1

0

7

7

.

3

0

7

7

.

4

2

1

0

1

.

0

8

1

1

0

.

8

5

1

1

2

.

3

7

1

1

2

.

8

8

1

2

5

.

3

2

1

5

5

.

6

2

1

5

6

.

3

9

1

6

1

.

5

2

1

6

2

.

5

6

1

9

5

.

9

8

OH

3

COO

SH

OH

3

COO

SH

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

f1 (ppm)

0

.

8

6

3

.

9

6

1

.

9

5

2

.

0

7

1

.

9

6

2

.

0

1

2

.

9

9

0

.

9

7

0

.

9

5

0

.

9

9

1

.

0

0

1

.

3

1

1

.

3

3

1

.

3

5

1

.

4

2

1

.

4

3

1

.

4

4

1

.

4

5

1

.

4

6

1

.

6

0

1

.

6

2

1

.

6

3

1

.

6

4

1

.

6

5

1

.

6

7

1

.

6

7

1

.

6

7

1

.

6

9

1

.

7

0

2

.

5

0

2

.

5

2

2

.

5

3

2

.

5

5

2

.

6

9

2

.

7

1

2

.

7

3

3

.

8

6

6

.

1

1

6

.

8

1

6

.

8

2

6

.

8

3

6

.

8

4

6

.

8

6

6

.

8

6

7

.

2

6

7

.

4

9

7

.

5

2

0102030405060708090100110120130140150160170180190200

f1 (ppm)

2

4

.

5

8

2

8

.

0

9

2

8

.

1

9

2

8

.

9

5

3

1

.

8

2

3

3

.

8

3

5

5

.

8

1

7

6

.

7

8

7

7

.

1

0

7

7

.

3

0

7

7

.

4

2

1

0

1

.

0

9

1

1

0

.

8

6

1

1

2

.

3

9

1

1

2

.

8

8

1

2

5

.

3

2

1

5

5

.

6

3

1

5

6

.

4

0

1

6

1

.

5

5

1

6

2

.

5

7