Coumarin-Pyrazole Hybrid with Red Shifted ESIPT emission and AIE characteristics – A comprehensive study
Milind R. Shreykara and NagaiyanSekara*
aDepartment of Dyestuff Technology, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai 400019, India.
Corresponding author. Tel.: +91 22 3361 2707; fax: +91 22 3361 1020; e-mail: ,
Supporting Information
List of Tables
Table S1. Charge transfer characteristics of CPM, CPA and CPI in different microenvironments.
Table S2. Computed bond lengths and dihedral angles of CPM, CPA and CPI in dimethylsulfoxide using B3LYP/6-31G(d) level of theory.
Table S3. Computed energy of CPI in S0 and S1 state, energy of HOMO-LUMO in Hartree (a.u.) and kcal/mol in ethanol and DMSO using B3LYP/6-31G(d) level of theory.
Table S4. Computed bond length alternation (BLA) index and bond order alternation (BOA) index of CPM, CPA and CPI in DMSO using B3LYP/6-31G(d) optimized geometries.
List of Figures
Fig.S5 Infrared spectra of 3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde 4
Figure S6 1H-NMR of 3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde4
Figure S7 13C-NMR of 3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde4
Figure S8 LC-MS of 3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde4
Fig.S9 Infrared spectra of2-((3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)methylene)malononitrile(CPM)
Figure S10 1H-NMR of 2-((3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)methylene)malononitrile(CPM)
Figure S11 13C-NMR of 2-((3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)methylene)malononitrile(CPM)
Fig.S12 Infrared spectra of(E)-2-(3-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)-1-phenylallylidene)malononitrile (CPA).
Figure S131H-NMR of (E)-2-(3-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)-1-phenylallylidene)malononitrile (CPA)
Figure S1413C-NMR of (E)-2-(3-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)-1-phenylallylidene)malononitrile (CPA).
Fig.S15 Infrared spectra of(E)-2-(3-(2-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-ylidene)malononitrile (CPI).
Figure S161H-NMR of (E)-2-(3-(2-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-ylidene)malononitrile (CPI).
Figure S17 13C-NMR of (E)-2-(3-(2-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-ylidene)malononitrile (CPI).
Table S1. Charge transfer characteristics of CPM, CPA and CPI in different microenvironments.
Dye / Solvents / a0[a] (cm) / 108 / Slope of LM / LMΔµeg[b] / 10-17Enol / Keto / Enol / Keto
CPM
Toluene / 5.59 / 5.61 / 2353.4 / 0.64 / 0.64
CHCl3 / 5.76 / 5.73 / 2353.4 / 0.67 / 0.66
EA / 5.66 / 5.64 / 2353.4 / 0.65 / 0.65
Dioxane / 5.63 / 5.64 / 2353.4 / 0.65 / 0.65
Acetone / 5.55 / 5.64 / 2353.4 / 0.63 / 0.65
EtOH / 5.6 / 5.66 / 2353.4 / 0.64 / 0.65
AcN / 5.62 / 5.70 / 2353.4 / 0.64 / 0.66
DMF / 5.64 / 5.61 / 2353.4 / 0.65 / 0.64
DMSO / 5.73 / 5.63 / 2353.4 / 0.66 / 0.65
CPA
Toluene / 6.15 / 6.10 / 12619 / 1.71 / 1.69
CHCl3 / 6.05 / 6.21 / 12619 / 1.67 / 1.73
EA / 6.19 / 6.15 / 12619 / 1.73 / 1.71
Dioxane / 5.97 / 6.04 / 12619 / 1.63 / 1.66
Acetone / 6.11 / 6.06 / 12619 / 1.69 / 1.67
EtOH / 5.99 / 6.13 / 12619 / 1.64 / 1.70
AcN / 6.07 / 6.12 / 12619 / 1.68 / 1.70
DMF / 6.09 / 6.07 / 12619 / 1.68 / 1.68
DMSO / 6.17 / 6.02 / 12619 / 1.72 / 1.65
CPI
Toluene / 6.18 / 6.06 / 6521.8 / 1.24 / 1.20
CHCl3 / 6.23 / 6.13 / 6521.8 / 1.25 / 1.22
EA / 6.14 / 6.32 / 6521.8 / 1.23 / 1.28
Dioxane / 6.26 / 6.29 / 6521.8 / 1.26 / 1.27
Acetone / 6.21 / 6.22 / 6521.8 / 1.25 / 1.25
EtOH / 6.13 / 6.28 / 6521.8 / 1.22 / 1.27
AcN / 6.29 / 6.26 / 6521.8 / 1.27 / 1.26
DMF / 6.46 / 6.13 / 6521.8 / 1.32 / 1.22
DMSO / 6.26 / 6.26 / 6521.8 / 1.26 / 1.26
[a]Onsager radius [b]Difference between ground and excited state dipole moments evaluated using Lippert-Mataga solvent polarity parameter.
Table S2.
Computed bond lengths and dihedral angles of CPM, CPA and CPI in dimethylsulfoxide using B3LYP/6-31G(d) level of theory.
Atom No / CPM / CPA / CPIS0[a] / S1[b] / S0[a] / S1[b] / S0[a] / S1[b]
E / K / E / K / E / K / E / K / E / K / E / K
Bond lengths
H13-O13a / 1.00 / 1.01 / 1.00 / 1.01 / 1.00 / 1.00
H13’-N17b / 1.05 / 1.03 / 1.05 / 1.03 / 1.05 / 1.04
H13’-O13c / 1.61 / 1.85 / 1.63 / 1.79 / 1.63 / 1.71
H13’-N17d / 1.71 / 1.69 / 1.71 / 1.68 / 1.71 / 1.68
C10-O13 / 1.33 / 1.26 / 1.31 / 1.25 / 1.33 / 1.26 / 1.32 / 1.25 / 1.33 / 1.26 / 1.32 / 1.25
Dihedral angles
H13'-O13-C10-C9a / 6.60 / 4.05 / 6.80 / 4.27 / 6.99 / 5.12
H13'-N17-C11-C9b / 11.26 / 13.99 / 12.98 / 12.79 / 13.01 / 14.23
C9-C11-N17-H13'a / 22.47 / 19.39 / 23.53 / 19.40 / 24.15 / 20.39
H13'-O13-C10-C9b / 0.92 / 7.47 / 1.78 / 3.20 / 1.30 / 1.39
C10-C9-C11-N17 / 21.93 / 10.80 / 20.87 / 24.62 / 23.21 / 12.43 / 20.34 / 19.07 / 23.82 / 12.71 / 20.24 / 15.88
[a]Enol form, [b]Keto form, [c]KetoSpacial, [d]EnolSpacial
Table S3.
Computed energy of CPI in S0 and S1 state, energy of HOMO-LUMO in Hartree (a.u.) and
kcal/mol in ethanol and DMSO using B3LYP/6-31G(d) level of theory.
Solvent / Ethanol / DMSOE / K / E / K / E / K
EM / S0 / -1640.41967 / -1640.41188 / -1640.42036 / -1640.4127
(Hartree) / S1 / -1640.33271 / -1640.32911 / -1640.33389 / -1640.3303
EM (kcal/mol) / S0 / -1029368.27 / -1029363.38 / -1029368.7 / -1029363.9
S1 / -1029313.7 / -1029311.43 / -1029314.43 / -1029312.2
ES0- ES1 / (kcal/mol) / -54.568941 / -51.9442026 / -54.2628576 / -51.705689
EH / (Hartree) / -0.21015 / -0.20731 / -0.21007 / -0.20724
(kcal/mol) / -131.869755 / -130.087647 / -131.819555 / -130.04372
EL / (Hartree) / -0.10125 / -0.10222 / -0.10133 / -0.10224
(kcal/mol) / -63.5346788 / -64.1433567 / -63.584879 / -64.155907
EL - EH / (kcal/mol) / 68.3350767 / 65.9442903 / 68.2346762 / 65.887815
E = Enol form, K = Keto form, EM = Energy of molecule, ES0 = energy at ground state, ES1 = energy at excited state, EH = Energy of HOMO, EL = Energy of LUMO.
Table S4. Computed bond length alternation (BLA) index and bond order alternation (BOA) index of CPM, CPA and CPI in DMSO using B3LYP/6-31G(d) optimized geometries.
Donor / Core selected / BLA index / BOA indexS0[a] / S1[b] / S0[a] / S1[b]
E / K / E / K / E / K / E / K
CPM
ESIPT / 0.033 / -0.047 / -0.014 / -0.058 / -0.336 / 0.051 / -0.097 / 0.098
N-Phenyl / -0.001 / -0.006 / 0.006 / -0.006 / -0.134 / -0.110 / -0.184 / -0.118
CPA
ESIPT / 0.034 / -0.046 / -0.008 / -0.070 / -0.336 / 0.043 / -0.131 / 0.159
N-Phenyl / 0.025 / 0.022 / 0.004 / 0.004 / -0.217 / -0.203 / -0.116 / -0.118
CPI
ESIPT / 0.034 / -0.044 / 0.012 / -0.070 / -0.338 / 0.035 / -0.229 / 0.163
N-Phenyl / 0.035 / 0.034 / -0.018 / -0.010 / -0.247 / -0.240 / 0.020 / -0.018
[a]Ground state, [b]excited state.
Fig.S5 Infrared spectra of 3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde 4
Figure S6 1H-NMR of 3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde4
Figure S7 13C-NMR of 3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde4
Figure S8 LC-MS of 3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde4
Fig.S9 Infrared spectra of2-((3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)methylene)malononitrile(CPM)
Figure S10 1H-NMR of 2-((3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)methylene)malononitrile(CPM)
Figure S11 13C-NMR of 2-((3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)methylene)malononitrile(CPM)
Fig.S12 Infrared spectra of(E)-2-(3-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)-1-phenylallylidene)malononitrile (CPA)..
Figure S131H-NMR of (E)-2-(3-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)-1-phenylallylidene)malononitrile (CPA).
Figure S1413C-NMR of (E)-2-(3-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)-1-phenylallylidene)malononitrile (CPA).
Fig.S15 Infrared spectra ofCPI.
Figure S161H-NMR of (E)-2-(3-(2-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-ylidene)malononitrile (CPI).
Figure S17 13C-NMR of (E)-2-(3-(2-(3-(4-hydroxy-2-oxo-2H-chromen-3-yl)-1-phenyl-1H-pyrazol-4-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-ylidene)malononitrile (CPI).