Chem. J. Chinese Universities ›› 2019, Vol. 40 ›› Issue (7): 1425.doi: 10.7503/cjcu20190127
• Physical Chemistry • Previous Articles Next Articles
LI Qing, YI Pinggui*(), TAO Hongwen, LI Yangyang, ZHANG Zhiyu, PENG Wenyu, LI Yuru
Received:
2019-02-28
Online:
2019-07-10
Published:
2019-07-12
Contact:
YI Pinggui
E-mail:pgyi@hnust.edu.cn
Supported by:
CLC Number:
TrendMD:
LI Qing, YI Pinggui, TAO Hongwen, LI Yangyang, ZHANG Zhiyu, PENG Wenyu, LI Yuru. Solvent and Substituent Effects on Spectral Characteristics and Excited-state Intramolecular Proton Transfer of 2-(2-Aminophenyl) Benzothiazole†[J]. Chem. J. Chinese Universities, 2019, 40(7): 1425.
Compound | Solvent | 1H NMR(500 MHz), δ |
---|---|---|
1(CH3) | DMSO-d6 | 8.75(d, —NH—, 1H), 8.10(d, 1H), 8.03(d, 1H),7.73(m, 1H), 7.53(t, 1H), 7.44(t, 1H), 7.39(t, 1H), 6.84(d, 1H), 6.72(t, 1H), 2.99(d, 3H) |
2(H) | DMSO-d6 | 8.09(t, 1H), 8.01(t, 1H), 7.64(t, 1H), 7.52(dd, 1H), 7.42(dd, 1H), 7.34(s, —NH2, 2H), 7.23(m, 1H), 6.89(t, 1H), 6.65(dd, 1H) |
3(COCH2Cl) | CDCl3 | 13.24(s, —NH—, 1H), 8.81(d, 1H), 8.05(d, 1H), 7.93(d, 1H), 7.88(d, 1H), 7.48(m, 2H), 7.44(t, 1H), 7.23(t, 1H), 4.31(s, 2H) |
4(COCH2Br) | CDCl3 | 13.06(s, —NH—, 1H), 8.75(d, 1H), 8.12(d, 1H), 7.94(d, 1H), 7.89(dd, 1H), 7.53(m, 2H), 7.45(t, 1H), 7.24(m, 1H), 4.15(m, 2H) |
5(COCH3) | CDCl3 | 12.38(d, —NH—, 1H), 8.78(d, 1H), 8.00(t, 1H), 7.92(d, 1H), 7.85(d, 1H), 7.53(t, 1H), 7.48(m, 1H), 7.43(d, 1H), 7.16(t, 1H), 2.33(m, 3H) |
6(COC2H5) | CDCl3 | 12.41(s, —NH—, 1H), 8.82(d, 1H), 8.00(d, 1H), 7.91(d, 1H), 7.84(d, 1H), 7.52(t, 1H), 7.47(t, 1H), 7.43(t, 1H), 2.59(m, 2H), 1.38(m, 3H) |
Table 1 1H NMR data of compounds 1―6
Compound | Solvent | 1H NMR(500 MHz), δ |
---|---|---|
1(CH3) | DMSO-d6 | 8.75(d, —NH—, 1H), 8.10(d, 1H), 8.03(d, 1H),7.73(m, 1H), 7.53(t, 1H), 7.44(t, 1H), 7.39(t, 1H), 6.84(d, 1H), 6.72(t, 1H), 2.99(d, 3H) |
2(H) | DMSO-d6 | 8.09(t, 1H), 8.01(t, 1H), 7.64(t, 1H), 7.52(dd, 1H), 7.42(dd, 1H), 7.34(s, —NH2, 2H), 7.23(m, 1H), 6.89(t, 1H), 6.65(dd, 1H) |
3(COCH2Cl) | CDCl3 | 13.24(s, —NH—, 1H), 8.81(d, 1H), 8.05(d, 1H), 7.93(d, 1H), 7.88(d, 1H), 7.48(m, 2H), 7.44(t, 1H), 7.23(t, 1H), 4.31(s, 2H) |
4(COCH2Br) | CDCl3 | 13.06(s, —NH—, 1H), 8.75(d, 1H), 8.12(d, 1H), 7.94(d, 1H), 7.89(dd, 1H), 7.53(m, 2H), 7.45(t, 1H), 7.24(m, 1H), 4.15(m, 2H) |
5(COCH3) | CDCl3 | 12.38(d, —NH—, 1H), 8.78(d, 1H), 8.00(t, 1H), 7.92(d, 1H), 7.85(d, 1H), 7.53(t, 1H), 7.48(m, 1H), 7.43(d, 1H), 7.16(t, 1H), 2.33(m, 3H) |
6(COC2H5) | CDCl3 | 12.41(s, —NH—, 1H), 8.82(d, 1H), 8.00(d, 1H), 7.91(d, 1H), 7.84(d, 1H), 7.52(t, 1H), 7.47(t, 1H), 7.43(t, 1H), 2.59(m, 2H), 1.38(m, 3H) |
Fig.1 Experimental(A) and calculated(B) absorption spectra of APBT in different solventsa. CYH; b. DCM; c. ACN; d. DMF; e. DMSO. Calculated at TD B3LYP/TZVP theoretical level.
Solvent | EK-E/(kJ·mol-1) | Ea/(kJ·mol-1) | EH-bond/(kJ·mol-1) | EHOMO/eV | ELUMO/eV | ΔEL-H/eV | |
---|---|---|---|---|---|---|---|
CYH | 85.8 | 80.6 | -6.7 | — | -5.668 | -1.769 | 3.899 |
DCM | 84.5 | 80.6 | -15.7 | -2.4 | -5.726 | -1.839 | 3.887 |
ACN | 84.2 | 80.6 | -18.5 | -8.7 | -5.621 | -1.841 | 3.780 |
DMF | 84.2 | 80.6 | -18.6 | -14.8 | -5.580 | -1.824 | 3.756 |
DMSO | 84.1 | 80.6 | -18.8 | -17.5 | -5.584 | -1.803 | 3.781 |
Table 2 Relative energies(EK-E) of keto form, active energies(Ea), solvation energies(Esolv), hydrogen bond energies(EH-bond), frontier molecular orbital energy levels(EHOMO, ELUMO) and their gaps(ΔEL-H) of ground state APBT in different solvents*
Solvent | EK-E/(kJ·mol-1) | Ea/(kJ·mol-1) | EH-bond/(kJ·mol-1) | EHOMO/eV | ELUMO/eV | ΔEL-H/eV | |
---|---|---|---|---|---|---|---|
CYH | 85.8 | 80.6 | -6.7 | — | -5.668 | -1.769 | 3.899 |
DCM | 84.5 | 80.6 | -15.7 | -2.4 | -5.726 | -1.839 | 3.887 |
ACN | 84.2 | 80.6 | -18.5 | -8.7 | -5.621 | -1.841 | 3.780 |
DMF | 84.2 | 80.6 | -18.6 | -14.8 | -5.580 | -1.824 | 3.756 |
DMSO | 84.1 | 80.6 | -18.8 | -17.5 | -5.584 | -1.803 | 3.781 |
Fig.2 Experimental and calculated fluorescence spectra of APBT in different solvents(A) Aprotic solvent: a. CYH; b. Diox; c. ACN; d. DMF; e. DMSO. (B) protic solvent: a. CYH; b. EtOH; c. MeOH; d. H2O. The solid line represents experimental spectra; the dotted line represents calculated spectra at TD B3LYP/TZVP theoretical level.
Solvent | Δ | AN1—C2—C3—C4/(°) | f | ||
---|---|---|---|---|---|
Enol* | Keto* | Enol* | Keto* | ||
CYH | 25.6 | 0 | 0 | 0.399 | 0.292 |
Diox | 39.2 | 0.1 | 0.4 | 0.398 | 0.313 |
ACN | 36.8 | 0 | 0.1 | 0.601 | 0.429 |
DMF | 41.2 | -2.6 | -13.7 | 0.588 | 0.398 |
DMSO | 42.4 | -3.0 | 12.9 | 0.578 | 0.400 |
EtOH | -14.8 | -21.0 | 98.1 | 0.496 | 0.001 |
MeOH | -14.3 | -22.7 | 97.8 | 0.490 | 0.001 |
H2O | -11.8 | -21.9 | -97.7 | 0.510 | 0.002 |
Table 3 Relative energies(ΔEK*-E*), dihedral angles(A) and oscillator strengths(f) of APBT in different solvents*
Solvent | Δ | AN1—C2—C3—C4/(°) | f | ||
---|---|---|---|---|---|
Enol* | Keto* | Enol* | Keto* | ||
CYH | 25.6 | 0 | 0 | 0.399 | 0.292 |
Diox | 39.2 | 0.1 | 0.4 | 0.398 | 0.313 |
ACN | 36.8 | 0 | 0.1 | 0.601 | 0.429 |
DMF | 41.2 | -2.6 | -13.7 | 0.588 | 0.398 |
DMSO | 42.4 | -3.0 | 12.9 | 0.578 | 0.400 |
EtOH | -14.8 | -21.0 | 98.1 | 0.496 | 0.001 |
MeOH | -14.3 | -22.7 | 97.8 | 0.490 | 0.001 |
H2O | -11.8 | -21.9 | -97.7 | 0.510 | 0.002 |
Fig.3 Experimental(a—d) and calculated(a’—d’) fluorescence spectra of APBT and its derivatives(A) a. 1(CH3); b. 2(H); c. 3(COCH2Cl); d. 4(COCH2Br). (B) a. 5(COCH3); b. 6(COC2H5). The solid line represents experimental spectra, dotted line represents calculated spectra at TD PBE1PBE/TZVP theoretical level in cyclohexane.
Compound | Tautomer | Δ | RN5—H6/nm | RN1—H6/nm | ∠N1—H6—N5/(°) | QN5/e | QH6/e |
---|---|---|---|---|---|---|---|
1(CH3) | Enol* | 28.9 | 0.104 | 0.175 | 143.4 | -0.616 | 0.437 |
Keto* | 0.164 | 0.108 | 139.5 | -0.672 | 0.468 | ||
2(H) | Enol* | 24.0 | 0.104 | 0.179 | 138.7 | -0.764 | 0.436 |
Keto* | 0.168 | 0.106 | 137.3 | -0.309 | 0.202 | ||
3(COCH2Cl) | Enol* | -11.2 | 0.105 | 0.171 | 144.8 | -0.600 | 0.453 |
Keto* | 0.198 | 0.103 | 124.3 | -0.673 | 0.494 | ||
4(COCH2Br) | Enol* | -8.0 | 0.105 | 0.170 | 145.5 | -0.633 | 0.442 |
Keto* | 0.201 | 0.102 | 123.0 | -0.732 | 0.477 | ||
5(COCH3) | Enol* | 7.0 | 0.105 | 0.171 | 146.0 | -0.606 | 0.445 |
Keto* | 0.183 | 0.104 | 132.3 | -0.691 | 0.482 | ||
6(COC2H5) | Enol* | 10.5 | 0.105 | 0.171 | 146.0 | -0.604 | 0.445 |
Keto* | 0.181 | 0.104 | 133.6 | -0.689 | 0.480 |
Table 4 Relative energies(EK*-E*) between keto and enol, selected bond lengths(R), bond angles and NBO charges(Q) of excited state APBT and its derivatives*
Compound | Tautomer | Δ | RN5—H6/nm | RN1—H6/nm | ∠N1—H6—N5/(°) | QN5/e | QH6/e |
---|---|---|---|---|---|---|---|
1(CH3) | Enol* | 28.9 | 0.104 | 0.175 | 143.4 | -0.616 | 0.437 |
Keto* | 0.164 | 0.108 | 139.5 | -0.672 | 0.468 | ||
2(H) | Enol* | 24.0 | 0.104 | 0.179 | 138.7 | -0.764 | 0.436 |
Keto* | 0.168 | 0.106 | 137.3 | -0.309 | 0.202 | ||
3(COCH2Cl) | Enol* | -11.2 | 0.105 | 0.171 | 144.8 | -0.600 | 0.453 |
Keto* | 0.198 | 0.103 | 124.3 | -0.673 | 0.494 | ||
4(COCH2Br) | Enol* | -8.0 | 0.105 | 0.170 | 145.5 | -0.633 | 0.442 |
Keto* | 0.201 | 0.102 | 123.0 | -0.732 | 0.477 | ||
5(COCH3) | Enol* | 7.0 | 0.105 | 0.171 | 146.0 | -0.606 | 0.445 |
Keto* | 0.183 | 0.104 | 132.3 | -0.691 | 0.482 | ||
6(COC2H5) | Enol* | 10.5 | 0.105 | 0.171 | 146.0 | -0.604 | 0.445 |
Keto* | 0.181 | 0.104 | 133.6 | -0.689 | 0.480 |
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