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Supporting Information for:
Arylamino-fluorene derivatives: optically induced electron transfer
investigation, redox-controlled modulation of absorption and
fluorescence
Agostina-Lina Capodilupo,a* Francesca Manni,a,b Giuseppina Anna Corrente,c Gianluca Accorsi,a
Eduardo Fabiano,d,e Antonio Cardone,f Roberto Giannuzzi,a Amerigo Beneduci,c* Giuseppe Gigli.a,g
a Institute of Nanotechnology (CNR-NANOTEC), c/o Campus Ecotekne, via Monteroni, Lecce 73100, Italy.b Dipartimento di Ingegneria dell’Innovazione, Universita del Salento, via Monteroni, Lecce 73100, Italy.c Department of Chemistry and Chemical Technologies, University of Calabria, Via P. Bucci, Cubo 15D, 87036 Arcavacata di Rende (CS), Italyd Institute for Microelectronics and Microsystems (CNR-IMM), c/o Campus Ecotekne, Via Monteroni, Lecce 73100, Italy. e Centre for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia (IIT), Via Barsanti, Arnesano, Lecce 73010, Italyf Institute of Chemistry of OrganoMetallic Compounds (CNR-ICCOM), Via Orabona, 4, 70125,
Bary, Italyg Dipartimento di Matematica e Fisica E. de Giorgi, Universita Del Salento, Campus Ecotekne, via Monteroni, Lecce, 73100, Italy
Corresponding authors:
Agostina-Lina Capodilupo, a* E-mail: [email protected]
Amerigo Beneduci,c* E-mail: [email protected]
Table of Contents
1. Photophysical characterizations, Figs. S1-S8.
2. Electrochemical characterizations, Figs. S9-S10.
3. Spectra Absorption by Chemical Oxidation, Figs. S11-S18.
4. Spectroelectrochemical measurements, Fig S15
5. Fit with Gaussian functions, Figs. S16-S17.
6. Fluorescence quenching by Chemical Oxidation, Figs S18-S21.
7. 1H and 13C-NMR spectra. Figs. S22-S45.
1. Photophysical characterizationSolvent: THF
Fig. S1 a) Absorption and b) Emission spectra of I, II and III in THF, at room temperature.
Fig. S2 a) Absorption and b) Emission spectra of IV, V and VI in THF, at room temperature.
Solvent: Methylcyclohexane
Fig. S3 a) Absorption and b) Emission spectra of I, II and III in MHC, at room temperature.
Fig. S4 a) Absorption and b) Emission spectra of IV, V and VI in MHC, at room temperature.
Solvent: DMSO
Fig. S5 a) Absorption and b) Emission spectra of I, II and III in DMSO, at room temperature.
Fig. S6 a) Absorption and b) Emission spectra of IV, V and VI in DMSO, at room temperature.
Solvent: ACN
Fig. S7 a) Absorption and b) Emission spectra of I, II and III in ACN, at room temperature.
Fig. S8 a) Absorption and b) Emission spectra of IV, V and VI in ACN, at room temperature.
2. Electrochemical Characterization
Fig. S9 DPV of II. Solvent CH2Cl2, supporting electrolyte 0.1 M TBAPF6. DPV condition:
modulation amplitude, 5 mV; modulation time, 0.05 s; interval time (Dt), 0.5 s, step potential (Estep),
0.005 V; scan rate, v = Estep/ Dt, 0.01 Vs-1.
Fig. S10 Cyclic voltammetry of IV (a) (50 mV/s); V (b) (50 mV/s); VI (c) (50 mV/s) at c = 10-3 M
in CH2Cl2/TBAPF6 (0.1 M) vs Ag/AgCl.
3. Spectra Absorption by Chemical Oxidation
Fig. S11 Absorption spectra of IV (a) and VI (b) in CH2Cl2 (4.1 × 10−5 M and 1.7 × 10−5,
respectively) while adding a solution of SbCl5 (1 mM) dropwise.
Fig. S12 Absorption spectra of I (a) and IV (b) in ACN (3.0 × 10−5 M and 4.2 × 10−5, respectively)
while adding a solution of CuClO4 (1 mM) dropwise.
Fig. S13 Absorption spectra of II (a) and V (b) in ACN (1.8 × 10−5 M and 3.0 × 10−5 M,
respectively) while adding a solution of CuClO4 (1 mM) dropwise.
Fig. S14 Absorption spectra of III (a) and VI (b) in ACN (1.3 × 10−5 M and 2.8 × 10−5 M,
respectively) while adding a solution of CuClO4 (1 mM) dropwise.
4. Spectroelectrochemical measurements
Fig. S15 Absorption spectral changes of I (a), II (b) and III (c) in CH2Cl2 solutions (ca. 0.2 mM)
and TBAPF6 (0.1 M). The potentials are referenced to the Ag/AgCl electrode.
5. Fit with Gaussian functions.
Fig. S16 Absorption spectra of the monocation of I+ in DCM and fit with Gaussian function. The
IV-CT band is given in red.
Fig. S17 Absorption spectra of the monocation of II+ (a) and III+ (b) in CH2Cl2 and fit with
Gaussian functions. The IV-CT band is given in blue.
6. Fluorescence quenching by Chemical Oxidation
Fig. S18 Fluorescence quenching of the II (a) (2.4 × 10−5 M in CH2Cl2) and V (b) (2.0 × 10−5 M in
CH2Cl2) upon SbCl5 titration (1.0 × 10−3 M in CH2Cl2).
Fig. S19 Correlation of fluorescent quenching trend of II (red line) and V (blue line) vs. equivalent
SbCl5 added.
Fig. S20 Fluorescence quenching of the III (a) (1.37 × 10−5 M in CH2Cl2) and VI (b) (4.3 × 10−5 M
in CH2Cl2) upon SbCl5 titration (1.0 × 10−3 M in CH2Cl2).
Fig. S21 Correlation of fluorescent quenching trend of III (red line) and VI (blue line) vs.
equivalent SbCl5 added.
7. 1H and 13C-NMR spectraCompound 1
Fig. S22. 1H NMR spectrum of compound 1 in CDCl3.
Fig. S23. 13C NMR spectrum of compound 1 in CDCl3.
Compound 2
Fig. S24. 1H NMR spectrum of compound 2 in CDCl3.
Fig. S25. 13C NMR spectrum of compound 2 in CDCl3.
Compound 3
Fig. S26. 1H NMR spectrum of compound 3 in Acetone.
Fig. S27. 1H NMR spectrum of compound 6 in Acetone.
Compound 4
Fig. S28. 1H NMR spectrum of compound 3 in Acetone.
Fig. S29. 1H NMR spectrum of compound 6 in Acetone.
Compound 5
Fig. S30. 1H NMR spectrum of compound 5 in Acetone.
Fig. S31. 13C NMR spectrum of compound 6 in Acetone.
Compound 6
Fig. S32. 1H NMR spectrum of compound 6 in Acetone.
Fig. S33. 13C NMR spectrum of compound 6 in Acetone.
Compound I
Fig. S34. 1H NMR spectrum of compound I in Acetone.
Fig. S35. 13C NMR spectrum of compound I in Acetone.
Compound II
Fig. S36. 1H NMR spectrum of compound I in Acetone.
Fig. S37. 13C NMR spectrum of compound II in Acetone.
Compound III
Fig. S38. 13H NMR spectrum of compound III in Acetone.
Fig. S39. 13C NMR spectrum of compound I in Acetone.
Compound IV
Fig. S40. 1H NMR spectrum of compound IV in Acetone.
Fig. S41. 1H NMR spectrum of compound IV in Acetone.
Compound V
Fig. S42. 1H NMR spectrum of compound V in Acetone.
Fig. S43. 13C NMR spectrum of compound V in Acetone.
Compound VI
Fig. S44. 1H NMR spectrum of compound VI in Acetone.
Fig. S45. 13C NMR spectrum of compound VI in Acetone.