Supplementary Information

Synthesis and photophysical properties of near infra-red absorbing

BODIPy derivatives and their nanoaggregates

Swati Dixita, Ankur Awasthia, Subhaprad Asha, Prabhat K. Singhb and Neeraj Agarwal

Contents:

Figure SI 1: Absorption spectra of (A) 1 and (B) 2 in acetonitrile and their nano-aggregates

Figure SI 2: Emission spectra of (A) 1 and (B) 2 in acetonitrile and their nano-aggregates. (C)

Full range absorption spectra of 2 (D) Excitation spectra of nanoaggregates of 2 monitored for

pyrene excimer.

Figure SI 3: Rayleigh Scattering data for (A) 1 and (B) 2 in acetonitrile and their nano-

aggregates

Figure SI 4: DLS data for nano-aggregates of 1. (A) Size distribution (B) Time correlation

Figure SI 5: DLS data for nano-aggregates of 2. (A) Size distribution (B) Time correlation

Figure SI 6: SEM images for nano-aggregates of (A) 1 and (B) 2.

Figure SI 7-8: 1H NMR and 13C NMR spectra of compound 1,2.

Figure SI 9: Absorption spectra of (A) 1 and (B) 2 in DMF recorded after regular time interval of red light irradiation.

Figure SI 10-17: Absorption spectra of a solution of 1 with DPBF in various solvents recorded after regular time interval of red light irradiation.

Figure SI 18: Comparison of singlet oxygen production of 2 in different solvents using DPBF as singlet oxygen acceptor

Figure SI 1: Absorption spectra of (A) 1 and (B) 2 in acetonitrile and their nano-aggregates.

Figure SI 2: Emission spectra of (A) 1 and (B) 2 in acetonitrile and their nano-aggregates. (C) Full range absorption spectra of 2 (D) Excitation spectra of nanoaggregates of 2 monitored for pyrene excimer.

DC

(A)… (B)

Figure SI 3: Rayleigh Scattering data for (A) 1 and (B) 2 in acetonitrile and their nano-aggregates.

Figure SI 4: DLS data for nano-aggregates of 1. (A) Size distribution (B) Time correlation

Figure SI 5: DLS data for nano-aggregates of 2. (A) Size distribution (B) Time correlation

Figure SI 6: SEM images for nano-aggregates of (A) 1 and (B) 2.

NMR

Figure SI 7: 1H NMR of 1 in CDCl3

Figure SI 8: 1H spectra of 2 in CDCl3

Photostability of 1 and 2:

(a) (b)

Figure SI 9: Absorption spectra of (A) 1 and (B) 2 in DMF recorded after regular time interval of red light irradiation.

Singlet oxygen production of compound 1 in Different solvents

Singlet oxygen generation of photosensitizers in different solvent were tested by trapping it with the widely used singlet oxygen acceptor 1, 3 – Diphenylisobenzofuran (DPBF). A solution of photosensitizer 3µM in different solvents (DCM, ethyl acetate, N,N-dimethyl formamide, acetone, toluene, methanol, water, dimethylsulfoxide.) was aerated for 10 min. The absorbance spectrum was taken and absorbance at 416 nm was noted as A0. DPBF was added to this solution such that the final concentration of DPBF in solution was 3 µM and the absorbance spectrum corresponding to time zero was recorded. The solution was then irradiated with red light (>600 nm) at 25ºC and absorption spectrum after every 2 minutes was recorded. This sequence of irradiation and absorption measurement continued for 20-24 min. Absorbance of DPBF at 416 nm (i.e. observed absorbance of solution – A0) was plotted against the time.

Figure SI 10: Absorption spectra of a solution of 1 with DPBF in DCM recorded after regular time interval of red light irradiation.

Figure SI 11: Absorption spectra of a solution of 1 with DPBF in ethyl acetate recorded after regular time interval of red light irradiation.

10

Figure SI 12: Absorption spectra of a solution of 1 with DPBF in N,N – dimethyl formamide recorded after regular time interval of red light irradiation.

Figure SI 13: Absorption spectra of a solution of 1 with DPBF in acetone recorded after regular time interval of red light irradiation.

Figure SI 14: Absorption spectra of a solution of 1 with DPBF in toluene recorded after regular time interval of red light irradiation.

Figure SI 15: Absorption spectra of a solution of 1 with DPBF in methanol recorded after regular time interval of red light irradiation.

Figure SI 16: Absorption spectra of a solution of 1 with DPBF in water recorded after regular time interval of red light irradiation.

Dimethyl sulfoxide

Figure SI 17: Absorption spectra of a solution of 1 with DPBF in dimethyl sulfoxide recorded after regular time interval of red light irradiation.

Comparison of singlet oxygen production of compound 2 in different solvents.

Figure SI 18: Comparison of singlet oxygen production of 2 in different solvents using DPBF as singlet oxygen acceptor