供电子基团修饰对NNI-R系列分子光物理性质的影响

doi:10.7503/cjcu20200086

摘要/Abstract

摘要：

设计了一系列具有不同供电子基团的N-苯基-1,8-萘二甲酰亚胺衍生物(NNI-R), 对它们在二氯甲烷和气相中的几何结构、电子结构以及室温磷光性能进行了研究. 在二氯甲烷极性溶剂中, NNI-R系列分子的最低单重激发态(S₁)有2个异构体, 分别表现为局域激发(LE)和电荷转移激发(CT). 具有弱给电子体(R=OMe, OH)时的NNI-R分子, 其S₁态为LE结构, 给体和受体间二面角垂直, 其总能量远低于CT结构, 会抑制系间窜越(ISC)的发生, 不会发生磷光现象. 在气相下, NNI-R系列分子的S₁态只有一种稳定的CT结构, 该特征能显著抑制荧光发射, 并有效促进系间窜越, 使NNI-R系列分子的室温磷光发射成为一种可能.

关键词: 室温磷光, 供电子基团, 电荷转移激发, 荧光速率, 系间窜越速率

Abstract:

A series of N-phenyl-1,8-naphthalimide derivatives with different electron donating groups(NNI-R) were designed and studied. The geometric and electronic structures as well as room phosphorescent performance were comparatively studied in dichloromethane solvent and the gas phase. It should be emphasized that in polar solvent(dichloromethane solvent), the NNI-Rs have two isomers of the S₁ state, one has charge-transfer(CT) character, the other has localized excitation(LE) feature. For NNI-R with R=OMe or OH, the total energy of the structure with LE character is far lower than the one of CT structure. which will inhibit intersystem crossing(ISC), and the room temperature phosphorescence will not happen. In the gas phase, all the first singlet excited states of NNI-R have only stable geometry with CT characters, which significantly inhibit the fluorescence(FL) rate and effectively promote the ISC rate. Phosphorescence emission becomes a possibility for NNI-R series molecules at room temperature. As a result, this work likes to contribute to a reliable theoretical basis for the synthesis and characterization of pure organic room temperature phosphorescent materials based on N-phenyl-1,8-naphthalimide.

Key words: Room temperature phosphorescence, Electron-donoring group, Charge-transfer excitation, Fluorescence rate, Intersystem crossing rate

中图分类号:

O641

TrendMD:

林桂锋,郭景富,何腾飞,任爱民. 供电子基团修饰对NNI-R系列分子光物理性质的影响. 高等学校化学学报, 2020, 41(6): 1277.

LIN Guifeng,GUO Jingfu,HE Tengfei,REN Aimin. Influences of Electron Donating Groups on the Photophysical Properties of NNI-R Series Molecules ^†. Chem. J. Chinese Universities, 2020, 41(6): 1277.

图/表 13

Fig.1 Chemical structures of NNI-R

Table 1 Dihedral angle and energy at optimized S1 of NNI-R

Molecule	Dihedral angle^a/(°)		Energy^b/eV
Molecule	LE	CT	LE	CT
NNI-OH	43.83	89.93	-26471.24	-26471.47
NNI-OMe	44.26	88.12	-27540.53	-27540.71
NNI-NH₂	47.19	90.04	-25931.10	-25930.92

Table 2 Bond length and dihedral angle between the donor and the acceptor, and the root mean square deviation(RMSD) at optimized S0 and S1 of NNI-R

Molecule	d(N2—C3)/nm			∠C1—N2—C3—C4/(°)			RMSD
Molecule	S₀	S₁	Δ(S₀-S₁)	S₀	S₁	Δ(S₀-S₁)	RMSD
NNI-H	0.14408	0.14399	0.00009	61.58	58.75	2.83	0.05
NNI-Me	0.14404	0.13706	0.00698	61.42	38.47	22.95	0.36
NNI-tBu	0.14401	0.13709	0.00692	61.34	38.59	22.75	0.36
NNI-OH	0.14393	0.13749	0.00644	61.17	39.06	22.11	0.29
NNI-OMe	0.14395	0.13762	0.00633	61.60	39.20	22.40	0.31
NNI-NH₂	0.14397	0.13848	0.00549	61.68	41.29	20.39	0.28
NNI-NMe₂	0.14396	0.13871	0.00525	62.02	41.52	20.50	0.34

Fig.2 Plots of frontier molecular orbitals, together with the HOMO, LUMO energy levels and their gaps at optimized S0 of NNI-R

Table 3 Calculated adiabatic energy difference(ΔEST) between S1 and T1/T2 state of NNI-R

Molecule	NNI-H	NNI-Me	NNI-tBu	NNI-OH	NNI-OMe	NNI-NH₂	NNI-NMe₂
$Δ E S 1 - T 2 / eV$	-0.3798	-0.2452	-0.2462	-0.2110	-0.2024	-0.1658	-0.1480
$Δ E S 1 - T 1 / eV$	-1.5268	-1.2703	-1.2769	-1.0584	-1.0064	-0.6765	-0.5221

Table 3 Calculated adiabatic energy difference(ΔEST) between S1 and T1/T2 state of NNI-R

Molecule	NNI-H	NNI-Me	NNI-tBu	NNI-OH	NNI-OMe	NNI-NH₂	NNI-NMe₂
$Δ E S 1 - T 2 / eV$	-0.3798	-0.2452	-0.2462	-0.2110	-0.2024	-0.1658	-0.1480
$Δ E S 1 - T 1 / eV$	-1.5268	-1.2703	-1.2769	-1.0584	-1.0064	-0.6765	-0.5221

Fig.3 Hole-electron distributions of NNI-Rs atoptimized S1 Blue: holes; green: electrons.

Table 4 Main parameters about the hole-electron distributions of NNI-R*

Molecule	$S m, index a$ /a.u.	$S r, index b$ /a.u.	$t c index$ /nm	$D d index$ /nm	Δ $σ e index$ /nm
NNI-H	0.66	0.87	-0.160	0.016	0.023
NNI-Me	0.14	0.33	0.229	0.426	0.040
NNI-tBu	0.14	0.33	0.229	0.428	0.038
NNI-OH	0.13	0.31	0.256	0.451	0.040
NNI-OMe	0.12	0.30	0.262	0.461	0.037
NNI-NH₂	0.11	0.28	0.297	0.499	0.033
NNI-NMe₂	0.10	0.26	0.322	0.529	0.021

Table 4 Main parameters about the hole-electron distributions of NNI-R*

Molecule	$S m, index a$ /a.u.	$S r, index b$ /a.u.	$t c index$ /nm	$D d index$ /nm	Δ $σ e index$ /nm
NNI-H	0.66	0.87	-0.160	0.016	0.023
NNI-Me	0.14	0.33	0.229	0.426	0.040
NNI-tBu	0.14	0.33	0.229	0.428	0.038
NNI-OH	0.13	0.31	0.256	0.451	0.040
NNI-OMe	0.12	0.30	0.262	0.461	0.037
NNI-NH₂	0.11	0.28	0.297	0.499	0.033
NNI-NMe₂	0.10	0.26	0.322	0.529	0.021

Table 5 Natural charge distribution of the substituents and the donor moieties atoptimized S0 and S1 state, and charge transfer from S0 to S1 state of NNI-R

Molecule	Charge[substituent, (-R)]/C			Charge[donor moiety, (Ph+R)]/C
Molecule	S₀	S₁	S₀→S₁	S₀	S₁	S₀→S₁
NNI-H	0.2131	0.2126	-0.0005	0.2590	0.2603	0.0013
NNI-Me	0.0432	0.0799	0.0367	0.2612	0.8103	0.5491
NNI-tBu	0.0192	0.0608	0.0416	0.2599	0.8111	0.5512
NNI-OH	-0.2106	-0.1212	0.0894	0.2605	0.8649	0.6044
NNI-OMe	-0.2250	-0.1135	0.1115	0.2616	0.8799	0.6183
NNI-NH₂	-0.0566	0.1350	0.1916	0.2654	0.9456	0.6802
NNI-NMe₂	-0.0553	0.1812	0.2365	0.2685	0.9712	0.7026

Fig.4 Charge change of substitutents and donor moieties during from S0 to S1 state and the change of Dindex a. NNI-Me; b. NNI-tBu; c. NNI-OH; d. NNI-OMe; e. NNI-NH2; f. NNI-NMe2.

Table 6 Calculated fluorescent rate(kFL), with the excitation energy(ΔE) and oscillator strength(f) of S1 state of NNI-R

Molecule	ΔE/eV	f	10^-7 k_FL/s^-1
NNI-H	3.57	0.2697	14.7556
NNI-Me	2.91	0.0093	0.3369
NNI-tBu	2.92	0.0091	0.3321
NNI-OH	2.71	0.0090	0.2823
NNI-OMe	2.66	0.0086	0.2604
NNI-NH₂	2.37	0.0075	0.1805
NNI-NMe₂	2.28	0.0066	0.1473

Table 7 Calculated spin-orbit coupling(SOC) matrix elements(cm-1) at optimized S1 geometry

Molecule	NNI-Me	NNI-tBu	NNI-OH	NNI-OMe	NNI-NH₂	NNI-NMe₂
<S₁\|Hso\| T₂>	0.6365	0.6769	0.4831	0.4576	2.2291	2.0871
<S₁\|Hso\| T₁>	3.1735	3.2833	2.7589	2.723	0.3552	0.3213

Fig.5 Hole-electron of NNI-R in S1, T1 and T2 state at optimized S1 state

Table 8 Calculated ISC rate(kISC) with the singlet-triplet energy gap(ΔEST), the reorganization energy(λ), and thespin-orbit coupling matrix element(VSOC)*

Molecule	ΔE_ST/eV	λ/eV	V_SOC/cm^-1	10^-7 k_ISC/s^-1	Molecule	ΔE_ST/eV	λ/eV	V_SOC/cm^-1	10^-7 k_ISC/s^-1
NNI-Me	-1.2703	0.6740	3.1735	1.8778	NNI-OMe	-1.0064	0.6559	2.7230	38.4418
NNI-tBu	-1.2769	0.6704	3.2833	1.6393	NNI-NH₂	-0.1658	0.1025	2.2291	275.8464
NNI-OH	-1.0584	0.6612	2.7589	23.8786	NNI-NMe₂	-0.1480	0.1716	2.0871	264.8364

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