Supporting Information

Corrole-Ferrocene & Corrole-Anthraquinone Dyads: Synthesis,

Spectroscopy and Photochemistry

Jaipal Kandhadi,a Venkatesh Yeduru,ab Prakriti R. Bangal.ab* Lingamallu Giribabu,ab*

*aInorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad-500007, Telangana, India.

*bAcademy of Scientific and Innovative Research (AcSIR), New Delhi, India.

Table of Contents Page No.

Fig. S1 ESI-MS spectrum of Cor-Fc. S1

Fig. S2 ESI-MS spectrum of Cor-AQ. S2

Fig. S31H NMR spectra of Cor-Fc (above) and Cor-AQ in CDCl3. The peak

labelled with asterisk (*) is due to solvent.S3

Fig. S4

Fig. S5

Absorption spectrum of Cor-Fc, Cor-AQ along with their constituent monomers in CH2Cl2.

Absorption spectrum of 1:1 mixture of (TTC+Fc) and (TTC+AQ-CHO) along with their constituent monomers in CH2Cl2.

S3

S3

Fig. S6 In-situ UV-Visible spectroelectrochemical changes of Cor-AQ at its first oxidation potential.

S4

Fig. S7In-situ UV-Visible spectroelectrochemical changes of Cor-AQ at its

second oxidation potential.S4

Fig. S8In-situ UV-Visible spectroelectrochemical changes of Cor-Fc during its

first oxidation potentialS5

Fig. S9In-situ UV-Visible spectroelectrochemical changes of Cor-Fc during its

second oxidation potential.S5

Fig. S10Geometrical optimized structure of Cor-AQ, optimized at the B3LYP/6-31G(d) level. S6

Fig. S11Geometrical optimized structure of Cor-Fc, optimized at the B3LYP/6-31G(d) level. S6

Fig. S12Fluorescence spectra λex= 425 nm of equi-absorbing solutions (O. D. λex =

S7

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2015

0.05).

Fig. S13Transient absorption spectra of TTC λPump =575 nm in ACN., Inset shows time profile at 480 nm. S8

Fig. S14 Kinetic at 435, 465 and 525 nm upon 410 nm excitation of TTC. S8

Fig. S15 Kinetic at 435, 465 and 525 nm upon 575 nm excitation of TTC. S9

Fig. S16Transient absorption Spectra of Cor-AQ dyad in ACN upon 575 nm

excitationS9

Fig. S17Probe wavelength dependent kinetic profile of Cor-AQ (A) and Cor-Fc

(B) dyads upon 410 nm excitation in ACN. S10

Fig. S18. Comparison of Cor-AQ fluorescence upconversion signal decay vs excited state absorption decay for two different excitations

Fig.S19 Comparison of Cor-Fc fluorescence upconversion signal decay vs excited state absorption decay for two different excitations

Fig.S20. Comparative analysis of transient absorption spectra of TTC 1ps after pump to EADS1 of Cor-AQ and Cor-FC. OD has been arbitrarily scaled for better comparison of spectral shape.

Fig.S21. Evolution-associated difference spectra (EADS) resulting from the global fitting applying a sequential model to the femtosecond transient absorption data of Cor-AQ (A) and Cor-Fc (B)

Figure S1. ESI-MS spectrum of [Cor-Fc].

S1

Figure S2. ESI-MS spectrum of [Cor-AQ].

Figure S3. 1H NMR spectra of Cor-Fc (above) and Cor-AQ in CDCl3. The peak labelled with asterisk (*) is due to solvent.

S2

Figure S4. Absorption spectrum of Cor-Fc, Cor-AQ along with their constituent monomers in CH2Cl2.

Figure S5. Absorption spectrum of 1:1 mixture of (TTC+Fc) and (TTC+AQ-CHO) along with their constituent monomers in CH2Cl2.

S3

Figure S6. In-situ UV-Visible spectroelectrochemical changes of (Cor-AQ) at its first oxidation potential.

Figure S7. In-situ UV-Visible spectroelectrochemical changes of (Cor-AQ) at its second oxidation potential.

S4

Figure S8. In-situ UV-Visible spectroelectrochemical changes of (Cor-Fer) during its first oxidation potential.

Figure S9. In-situ UV-Visible spectroelectrochemical changes of (Cor-Fc)during its second oxidation potential.

S5

Figure S10. Geometrical optimized structure of (Cor-AQ), optimized at the B3LYP/6-31G(d)level.

Figure S11. Geometrical optimized structure of (Cor-Fc), optimized at the B3LYP/6-31G(d) level.

S6

Figure S12. Fluorescence spectra λex= 425 nm of equi-absorbing solutions (O. D. λex = 0.05).

S7

450 500 550 650

-0.02

0.00

0.02

0.04

0 2 4 6 8 100.0000.0050.0100.0150.0200.0250.030

OD

Time (ps)

OD

Wavelength (nm)

BL 0 ps 0.5 ps 10 ps

Figure S13. Transient absorption spectra of TTC λPump =575 nm in ACN., Inset shows time profile at 480 nm.

1.0

0.5

0.0

Nor

m.

OD

Time (ns)

0.5

0.0

1.0

0.5

0.0

2 4 6

Probe=525 nm

Probe=435 nm

Probe=460 nm

Figure S14. Kinetic at 435, 465 and 525 nm upon 410 nm excitation of TTC in 6.5 ns time window..

S8

302010

0

m

OD

1086420Time (ps)

302010

0

1612

840

806040200Time (ps)

Probe=435 nm

Probe=465 nm

Probe=525 nm

Figure S15. Kinetic at 435, 465 and 525 nm upon 575 nm excitation of TTC.

450 500 550 600 650

-0.015

-0.010

-0.005

0.000

0.005

OD

Wavelength (nm)

0 ps 1 ps 5 ps 10 ps 15 ps

Figure S16. Transient absorption Spectra of Cor-AQ dyad in ACN upon 575 nm excitation.

S9

0 50 100 150 2000.0

0.5

1.0

Time (ps)

Probe @ 470 nm

0.0

0.5

1.0Probe @ 480 nm

Norm

alize

d O

D 0.0

0.5

1.0

Probe @ 500 nm

2 4 6 8 10 12 140.0

0.5

1.0

Time (ps)

Probe@ 470 nm

0.0

0.5

1.0

Norm

. OD Probe @ 480 nm

0.0

0.5

1.0

Probe@ 500 nm(A)

(B)

Figure S17. Probe wavelength dependent kinetic profile of (Cor-AQ) (A) and (Cor-Fc) (B) dyads upon 410 nm excitation in ACN.

S10

1.0

0.5

0.0Nor

m. C

ount

10987654321Time (ps)

1.0

0.5

0.0

O

D

1.0

0.5

0.0

FU Profile at 670 nm, Ex=410 nm

ESA at 515 nm, Ex=410 nm

ESA at 515 nm, Ex=575 nm

Figure S18. Comparison of Cor-AQ fluorescence up-conversion signal decay vs excited state absorption decay for two different excitations .

1.0

0.5

0.0Nor

m. C

ount

10987654321Time (ps)

1.0

0.5

0.0

Norm

.

OD

1.0

0.5

0.0

Fl profile at 670 nm, Ex=410 nm

ESA at 515 nm, Ex=410 nm

ESA at 515 nm, Ex=410 nm

Figure S19. Comparison of Cor-Fc fluorescence upconversion signal decay vs excited state absorption decay for two different excitations.

S11

450 500 550 600 650

-1.0

-0.8

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

OD

Wavelength (nm)

EADS1, Cor-AQ ESA TTC after 1 ps EADS1 Cor-Fc

Figure S20. Comparative analysis of transient absorption spectra of TTC 1ps after pump to EADS1 of Cor-AQ and Cor-FC. OD has been arbitrarily scaled for better comparison of spectral shape.

EADS1EADS2EADS3

EADS1EADS2EADS3

(A)

(B)

Figure S 21. Evolution-associated difference spectra (EADS) resulting from the global fitting applying a sequential model to the femtosecond transient absorption data of Cor-AQ (A) and Cor-Fc (B)

S12