Synthesis， Luminescence and Electrochemical Properties of Bis-Triphenylamine-Based Small Molecules and Electrochemical Polymers Connected by Flexible Chains

doi:10.19894/j.issn.1000-0518.240260

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (3): 353-364.DOI: 10.19894/j.issn.1000-0518.240260

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Synthesis， Luminescence and Electrochemical Properties of Bis-Triphenylamine-Based Small Molecules and Electrochemical Polymers Connected by Flexible Chains

Hong-Yu SHI¹^,², Dong-Xing TAN¹(), Fu-She HAN¹^,²()

^1.The Laboratory of Green Chemistry and Process，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^2.School of Applied Chemistry and Engineering，University of Science and Technology of China，Hefei 230026，China

Received:2024-08-12 Accepted:2025-02-06 Published:2025-03-01 Online:2025-04-11
Contact: Dong-Xing TAN,Fu-She HAN
About author:fshan@ciac.ac.cn
dxtan@ciac.ac.cn；

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Abstract

Abstract:

Three bis-triphenylamine small molecules 1-3 linked by flexible amides or ester chains were designed and synthesized. The corresponding electrochemical polymer films were prepared by electrochemical polymerization （EP）. Following which， the photoluminescence （PL） and electrochemiluminescence （ECL） properties of the small molecules and polymers were studied. The solutions and solids of three small molecules， and their corresponding polymers exhibited strong photoluminescence in the blue region of 407~468 nm. The relative fluorescence quantum yields of compounds 1-3 in CH₂Cl₂ are 77%， 97% and 84%， respectively. Using tripropylamine as a co-reactant， the small molecule solid films of the three compounds exhibit general to good ECL with relative quantum yields of 0.52%， 55.58% and 16.82%， respectively. Comparative analysis revealed that compound 2 displayed the strongest photoluminescence and electrochemiluminescence， while compound 1 showed the weakest property. Based on the ¹H NMR spectroscopic analyses by varying the concentrations， compound 1 exhibits strong intermolecular hydrogen bonding， while compound 2 exhibits strong intramolecular hydrogen bonding. The difference in luminescence efficiency may be caused by different modes of intermolecular and intramolecular hydrogen bonding interactions. Finally， both the small molecule solid film and EP film of compound 2 could be used as an ECL luminophore for detection of dopamine （DA）， with a limit of detection （LOD） of 0.43 and 1.51 μmol/L， respectively.

Key words: Bis-triphenylamine, Electrochemical polymer film, Photoluminescence, Electrochemiluminescence, Detection of dopamine

CLC Number:

O625.6

Hong-Yu SHI, Dong-Xing TAN, Fu-She HAN. Synthesis， Luminescence and Electrochemical Properties of Bis-Triphenylamine-Based Small Molecules and Electrochemical Polymers Connected by Flexible Chains[J]. Chinese Journal of Applied Chemistry, 2025, 42(3): 353-364.

Figures/Tables 11

Fig.1 Synthetic routes of compounds 1-3

Fig.2 CV profiles （1st and 2nd cycle） of compounds 1 （A）， 2 （B） and 3 （C） and CV profiles （1st to 15th cycles） of compounds 1 （D）， 2 （E） and 3 （F） in CH2Cl2 in the presence of TBAP （0.1 mol/L） electrolyte at room temperature under argon protection. Scan rate： 100 mV/s； Scan range： 0 to 1.60 V

Table 1 Electrochemical data and theoretical calculation results of compounds 1-3 in CH2Cl2 （0.1 mol/L TBAP）

Compounds	E_onset/V ^a	HOMO/eV	LUMO/eV	$E_{g}^{o p t}$ /eV ^e	$E_{g}^{c a l}$ /eV ^c
1	1.06	-5.41 ^b /-4.86 ^c	-2.04 ^d /-1.03 ^c	3.37	4.18
2	1.10	-5.45/-5.17	-2.13/-1.24	3.32	3.99
3	1.16	-5.51/-5.57	-2.16/-1.30	3.35	4.02

Table 1 Electrochemical data and theoretical calculation results of compounds 1-3 in CH2Cl2 （0.1 mol/L TBAP）

Compounds	E_onset/V ^a	HOMO/eV	LUMO/eV	$E_{g}^{o p t}$ /eV ^e	$E_{g}^{c a l}$ /eV ^c
1	1.06	-5.41 ^b /-4.86 ^c	-2.04 ^d /-1.03 ^c	3.37	4.18
2	1.10	-5.45/-5.17	-2.13/-1.24	3.32	3.99
3	1.16	-5.51/-5.57	-2.16/-1.30	3.35	4.02

Fig.3 Normalized absorption and PL spectra of 1 （A， D）， 2 （B， E） and 3 （C， F） in solvents with different polarities

Table 2 The absorption （λab） and emission （λPL） date of compounds 1-3 in different solvents

Compounds	Solvents	λ_ab/nm ^a	10^-4ε/（L·mol^-1·cm^-1）	λ_PL/nm ^b	Δλ/nm ^c
1	n-Hex	330/300	2.53/2.37	385	55
	Tol	332/308	4.09/3.68	410	78
	THF	325/305	2.95/2.75	442	117
	DCM	331/306	2.86/2.45	443	112
	DMF	326/307	3.65/3.42	442	116
2	n-Hex	331/302	2.08/1.73	402	71
	Tol	333/304	3.31/2.66	428	95
	THF	330/304	2.94/2.65	447	117
	DCM	334/305	3.93/3.00	462	128
	DMF	330/305	3.36/2.82	467	137
3	n-Hex	335/300	3.41/2.42	387	52
	Tol	341/304	4.01/2.70	415	74
	THF	334/307	3.47/2.32	433	99
	DCM	336/302	3.07/1.96	451	115
	DMF	334/302	3.51/2.42	465	131

Fig.4 Possible hydrogen bonding modes of compounds 1 and 2

Fig.5 PL spectra of compounds 1 （A）， 2 （B） and 3 （C） in THF/water mixtures with different water volume fractions （φ（water））. Plots of the relative PL intensity （I/I0 ） versus water volume fractions （φ（water）） of compounds 1， 2 and 3 （D）. I0 denotes emission intensity in pure THF. Concentration： 10 μmol/L

Fig.6 PL emission spectra of solid （A） and EP films （B） of compounds 1-3. Insert： solid and EP films under UV light of 365 nm

Fig.7 Optimized geometries and molecular orbitals of HOMO and LUMO levels of the molecules

Fig.8 ECL stability of the solid films of compounds 1 （A）， 2 （B） and 3 （C）； ECL spectra of the solid films （D）， PMT=800 V

Fig.9 Stern-Volmer charts of I0/（I-1） of the solid and EP film versus the concentration of DA （A， D）. The linear plots of the solid and EP film between the ECL intensity and the DA concentration （B， E）. ECL intensity of the solid and EP film with different analytes with （red） and without （black） the addition of 100 μmol/L DA （C， F）

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Synthesis， Luminescence and Electrochemical Properties of Bis-Triphenylamine-Based Small Molecules and Electrochemical Polymers Connected by Flexible Chains

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