FerriNaphth: A Fluorescent Dosimeter for Redox Active Metals

Transcription

1 Supporting Information FerriNaphth: A Fluorescent Dosimeter for Redox Active Metals Randy K. Jackson, Yu Shi, Xudong Yao and Shawn Burdette * Department of Chemistry, University of Connecticut, 55 North Eagleville Road U-36, Storrs, Connecticut 6269 shawn.burdette@uconn.edu II. III. NMR spectra...s1 Additional spectroscopic data...s5

2 I. NMR spectra N HN

3 N HN

4 N HN H H

5 N HN H H

6 .2 1 µm FN 1 µm FN+ 2 eq Fe III.15 Absorbance Figure S-1. xidation of FerriNaphth with Fe III in methanol. The spectrum of a 1 µm solution of FerriNaphth in methanol was recorded followed by the addition of 2 equivalents of Fe(N 3 ) 3. The solution was allowed to equilibrate for two minutes followed by the acquisition of spectra taken until there was no further change.

7 Absorbance µm FerriNaphth 1 µm FN+ 5. µm Cu II 1 µm FN+ 1 µm Cu II 1 µm FN+ 15µM Cu II 1 µm FN +2 µm Cu II 1 um FN+24µM Cu II 1 µm FN+ 24 µm Cu II Figure S-2. xidation of FerriNaphth with incremental additions of Cu(N 3 ) 2 in acetonitrile. Metal from a 1 mm stock solution was added to a 1 µm solution of FerriNaphth in 2.5 µm increments. Absorption measurements were recorded after no additional changes were observed following the addition of metal.

8 .25 1µM FerriNaphth FerriNaphth + 2 eq Cu II.2 Absorbance Figure S-3. xidation of FerriNaphth with Cu II in methanol. The absorption of a 1 µm solution of FerriNaphth was measured followed by the addition of 2 equivalence of Cu(N 3 ) 2 from a 1 mm stock solution in 6/4 EtH/CH 3 CN. The spectrum of the equilibrated mixture was taken after three minutes and subsequent measurements were taken to ensure no further changes.

9 Absorbance µm FerriNahth 1 µm Ga III 2 µm Ga III 4 µm Ga III 6 µm Ga III 7 µm Ga III 8 µm Ga III 9 µm Ga III 1 µm Ga III 12 µm Ga III 14 µm Ga III 16 µm Ga III 18 µm Ga III 2 µm Ga III Figure S-4. UV-vis titration of 1 µm FerriNaphth with Ga(N 3 ) 3 in methanol. Metal was added in 2 µm increments (6µL aliquots) from a 1 mm stock solution. Each spectrum was corrected for dilution by multiplying measured absorption by the inverse of the dilution factor.

10 Absorbance µm FN 1 µ M FN +2.5 µm Fe III 1 µm FN + 1. µm Fe III 1 µm FN + 15 µm Fe III 1 µm FN +2 µm Fe III 1 µm FN + 21 µm Fe III 1µ M FN + 23 µm Fe III 1 µm FN + 25 µm Fe III 1 µm FN + 26 µm Fe III Figure S-5. xidation of FerriNaphth with incremental additions of Fe(N 3 ) 3 in methanol. Iron from a 1 mm stock solution was added to a 1 µm solution of FerriNaphth in 2.5 µm increments up to 2 equivalents. An additional.6 equivalents were added incrementally to complete the oxidation. Absorption measurements were recorded after no additional changes were observed following the addition of metal.

11 Intensity a.u 15 1 Initial 8 min 16 min 24 min 32 min 4 min 48 min Figure S-6. Emission spectra of oxidation of 1 µm FerriNaphth in methanol with 2 equivalents of Fe(N 3 ) 3. Spectra were recorded over a period of 48 min. Excitation was provided at 4 nm with an excitation slit width of 5. nm and an emission slit width of 1 nm.

12 Absorbance µm 6.7 µm 4.4 µm 3. µm 2. µm 1.3 µm.86 µm.57 µm Figure S-7. xidation of 1 µm of FerriNaphth with 2 equivalents of Fe(N 3 ) 3 at different concentrations of probe in acetonitrile.

13 Absorbance at 368 nm Concentration / 1-6 M Figure S-8. concentration. Absorption of species formed at 368 nm, plotted as a function of

14 µm Fe(N ) in MEH µm Fe(N ) in CH CN µm FeCl in CH CN µm FeCl in MEH 3 Absorbance Figure S-9. Absorption spectra of 2 µm Fe(N 3 ) 3 and 2 µm FeCl 3 in methanol and acetonitrile.