dqgwkh ...fluorescence sensing and intracellular imaging of pd2+ ion by a novel coumarinyl-rhodamine...

Fluorescence sensing and intracellular imaging of Pd2+ ion by a novel

coumarinyl-rhodamine Schiff base†

Arup Kumar Adak, Saikat Manna, Bankim Chandra Ghosh, Sudipta Pathak, Rakesh Purkait and

Chittaranjan Sinha

O NN

N

ONH2

CHOOHO

Me

O

O NN

N

ON

OHO

Me

O

Ethanol, Reflux

HCR

A

B

CHOOHO

Me

O

O NN

N

ONH2

OHO

Me

OOHHO

O NN

COOH

Cl

A

B

i ii

iii

Scheme S1: Structure and synthesis of sensor HCR where (i). Ethyl acetoacetate, Conc. H2SO4;

(ii). Hexamine, Acetic acid; (iii). Excess Ethelene diamine, EtOH, Reflux.

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019

Figure S1. FTIR spectrum of HCR.

Absorption, cm-1 Assignments

~3400

2970.18

~2800

1727.39

1668.08

1614.36

~1600

1512.24

1218.35

O – H stretching (broad and very weak)

C-H stretching (Ar-H)

C – H stretching (-CH3 and –CH2-)

C=O stretching (α,β-unsaturated δ-lactone.

C=O stretching (α, β-unsaturated-5-membered amide or -lactam).

C = N stretching (Schiff’s base)

C = C stretching (aromatic ring)

C – N stretching.

C – O – C stretching (aromatic ether)

Figure S2. Mass spectrum of HCR.

Figure S3. 1H NMR spectrum of HCR in CDCl3 solution.

Figure S4. 13C NMR spectrum of HCR in CDCl3 solution.

Fig. S5 The linear dynamic response of HCR for Pd2+ and the determination of the limit of detection (LOD) of Pd2+.

Figure S6: Job’s plot of HCR and Pd2+ reaction and associated absorbance change

Y = A + B*X

Y= (0.596 10-5± 0.060) + (1.099 ± 0.185) *

Figure S7. Benesi-Hildebrand plot obtained from the fluorescence titration data

Figure S8. FTIR spectrum of [CR--Pd2+]+ complex in KBr pellete

Figure S9. ESI-MS spectrum of [CR--Pd2+]+

Figure S10. Cellular image after treatment with HCR (5 M)

Table S1 Frontier molecular orbitals contributions of HCR

MO Energy (eV) Rodamine CoumarineLUMO+10 0.76 96 4LUMO+9 0.51 38 62LUMO+8 0.46 83 17LUMO+7 0.25 2 98LUMO+6 0.06 100 0LUMO+5 -0.18 100 0LUMO+4 -0.24 99 1LUMO+3 -0.36 8 92LUMO+2 -0.81 95 5LUMO+1 -1.0 20 80LUMO -2.03 1 99HOMO -4.94 100 0HOMO-1 -5.21 100 0HOMO-2 -5.76 100 0HOMO-3 -6.17 95 5HOMO-4 -6.41 86 14HOMO-5 -6.44 96 4HOMO-6 -6.5 2 98HOMO-7 -6.77 97 3HOMO-8 -6.89 91 9HOMO-9 -6.92 65 65HOMO-10 -7.04 97 3

Table S2 Frontier molecular orbitals contributions of [CR--Pd2+]+

MO Energy (eV) Pd Rodamine CoumarineLUMO+10 -1.66 34 62 4LUMO+9 -1.82 3 3 95LUMO+8 -2.7 0 100 0LUMO+7 -2.79 0 100 0LUMO+6 -3.02 0 100 0LUMO+5 -3.25 0 100 0LUMO+4 -3.36 1 4 95LUMO+3 -3.82 2 91 6LUMO+2 -3.93 3 25 72LUMO+1 -4.32 55 34 10LUMO -5.26 0 100 0HOMO -7.58 7 7 86HOMO-1 -8.07 0 100 0HOMO-2 -8.46 21 56 23HOMO-3 -8.61 20 24 57HOMO-4 -8.81 27 65 7HOMO-5 -8.89 50 46 4HOMO-6 -9.08 31 39 30HOMO-7 -9.22 2 7 92HOMO-8 -9.33 9 33 59HOMO-9 -9.5 4 73 23HOMO-10 -9.71 15 61 24