Influences of Electron Donating Groups on the Photophysical Properties of NNI-R Series Molecules †

doi:10.7503/cjcu20200086

Abstract

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

CLC Number:

O641

TrendMD:

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

Figures/Tables 13

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

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

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

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

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

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

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

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

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

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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