Addition/Correction pubs.acs.org/JPCC
Correction to “Insights into the Photobehavior of Fluorescent Oxazinone, Quinazoline, and Difluoroboron Derivatives: Molecular Design Based on the Structure−Property Relationships” Jianyong Yuan, Yizhong Yuan,* Xiaohui Tian,* Yidan Liu, and Jinyu Sun J. Phys. Chem. C 2017, 121 (14), pp 8091−8108. DOI: 10.1021/acs.jpcc.7b01360 S Supporting Information *
its large emission reorganization (0.40 eV), results in the largest Stokes shift (10.9 × 103 cm−1) among all series. The BOA(vacu) and ΔBOA values of Qui-H-OCH3 (0.2975 and 0.0116) in original Table 1 should be 0.3091 and 0.0001, respectively; meanwhile, the m7 value (1.3264, in a vacuum) of Qui-H-OCH3 in original Table S2 should be 1.3727. Therefore, a corrected Figure 2b is presented here to accord with these corrections.
T
he reorganization energies in original Table 8 are erroneous due to the inconsistency of calculation levels, and therefore we give a corrected version of reorganization energies below. Both E0(GS) and E0(ES) are calculated at the B3LYP/ 6-311G(d) level in ethanol, while E1(GS) and E1(ES) are evaluated according to E1(GS) = E0(GS) + Ecal exc (LC-ω*PBE) and E1(ES) = E0(ES) + Ecal (LC-ω*PBE). Note that in the oxazinone series emi cal we use Ecal emi(PCM-tuned LC-ω*PBE) instead of Eemi(LC-ω*PBE) to obtain accurate E1(ES) values. Moreover, the first excitation energy of Oxa-Cl-OCH3-BF2 [Ecal exc(LC-ω*PBE, S1)] is 3.18 eV. Eventually, the emission and absorption reorganization energies [ΔE(emi) and ΔE(abs)] are given by ΔE(emi) = E0(ES) − E0(GS) and ΔE(abs) = E1(GS) − E1(ES), respectively (Figure S9). From the corrected Table 8, we can find in the oxazinone series that the absorption part owns the majority of the total reorganization energy (77−80%), while the emission part gains the minority (20−23%). With respect to the quinazoline series, the absorption and emission parts contribute equally to the total reorganization energy (i.e., ∼50% for each part). However, in the case of the difluoroboron series, the emission part governs the total reorganization energy (76% and 56% for Oxa-Cl-OCH3-BF2 and Qui-Cl-OCH3-BF2, respectively), whereas the absorption part contributes the minority (24% and 44%). Therefore, the large Stokes shifts of the oxazinone, quinazoline, and difluoroboron series (except Oxa-Cl-OCH3-BF2) are mainly attributed to the large absorption reorganizations, joint absorption and emission reorganizations, and predominant emission reorganizations, respectively. As for Oxa-Cl-OCH3-BF2, the extremely higher energy loss of internal conversion of S2 → S1 (0.82 eV), along with
Figure 2. Solvent effect (ethanol) on (b) the Mayer bond orders of the oxazinone, quinazoline, and difluoroboron series in the ground states. More details were collected in Table S2.
Table 8. Corrected Reorganization Energies [ΔE(emi) and ΔE(abs)] of the Oxazinone, Quinazoline, and Difluoroboron Series between S1 and S0 in Ethanol compound
E0(GS) (au)
E1(GS) (au)
E0(ES) (au)
E1(ES) (au)
ΔE(emi) (eV)
ΔE(abs) (eV)
ΔE(emi) + ΔE(abs) (eV)
Oxa-H-CH3 Oxa-Cl-CH3 Oxa-H-OCH3 Oxa-Cl-OCH3 Oxa-Cl-OCH3-BF2 Qui-H-CH3 Qui-Cl-CH3 Qui-H-OCH3 Qui-Cl-OCH3 Qui-Cl-OCH3-BF2
−1618.748888 −2537.990712 −1693.977547 −2613.219372 −2837.386444 −1808.884395 −2728.127357 −1884.113006 −2803.356078 −3027.525170
−1618.610979 −2537.859763 −1693.840689 −2613.089713 −2837.269691 −1808.748129 −2727.995794 −1883.977335 −2803.224783 −3027.411221
−1618.739474 −2537.981585 −1693.968305 −2613.210536 −2837.371690 −1808.865677 −2728.109133 −1884.094360 −2803.337651 −3027.506884
−1618.642088 −2537.891917 −1693.875330 −2613.124175 −2837.274304 −1808.767924 −2728.014320 −1883.996240 −2803.243205 −3027.425668
0.26 (23%) 0.25 (22%) 0.25 (21%) 0.24 (20%) 0.40 (76%) 0.51 (49%) 0.50 (50%) 0.51 (50%) 0.50 (50%) 0.50 (56%)
0.85 (77%) 0.87 (78%) 0.94 (79%) 0.94 (80%) 0.13 (24%) 0.54 (51%) 0.50 (50%) 0.51 (50%) 0.50 (50%) 0.39 (44%)
1.10 1.12 1.19 1.18 0.53 1.05 1.00 1.02 1.00 0.89
© XXXX American Chemical Society
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DOI: 10.1021/acs.jpcc.7b03508 J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
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Addition/Correction
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.7b03508.
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AUTHOR INFORMATION
Corresponding Authors
*Y.-Z.Y. E-mail:
[email protected]. *X.-H.T. E-mail:
[email protected].
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DOI: 10.1021/acs.jpcc.7b03508 J. Phys. Chem. C XXXX, XXX, XXX−XXX
