Synthesis and Characterization of New Indeno[1,2-b]fluorene-6,12-dione Derivatives

doi:10.6023/cjoc202206038

Abstract

Indeno fluorene-6,12-dione derivatives 5 modified by different alkyl substitutions were designed and synthesized from 2,5-dibromo-p-xylene and phenylboronic acid derivatives through oxidation, esterification, Suzuki coupling, saponi- fication and cyclization reactions. Alkyl chains of different lengths were introduced into molecules to improve the solubility of the compounds and investigate the effects of systematic substitution variation on their properties. It was found that the solubility, thermal and optical stability of the new compounds were better than those of pentacene. Compounds 5 have increased electronegativities because of the low lowest unoccupied molecular orbital (LUMO) energies (≤–3.4 eV). 2,8- Diisopropylindeno[1,2-b]fluorene-6,12-dione (5b) and 2,8-dibutylindeno[1,2-b]fluorene-6,12-dione (5c) have rigid molecular frameworks and pack into slipped face-to-face π-stacks, the layer spacings are 0.3457 and 0.3423 nm, respectively. The molecular packing could facilitate carrier transport. The properties of these new materials indicate that they are good candidates for applications in organic optoelectronics.

Key words: indeno[1,2-b]fluorene, organic semiconductor, Suzuki coupling reaction, crystal structure, rigid framework

Cite this article

Jing Wang, Linlin Wu, Qian Wang. Synthesis and Characterization of New Indeno[1,2-b]fluorene-6,12-dione Derivatives[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 223-228.

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Fig. & Tab. 7

Scheme 1. Synthetic route to compounds 5a~5d

Figure 1. Normalized UV-Vis absorption spectra in dichloromethane (DCM) of 5a~5d (10 μmol /L)

Compound	λ_abs/nm	E_g^a/eV	λ_em/nm	T_dec/℃	E_ox/V	Eonset ox/V	E1 red/V	E2 red/V	Eonset red/V	E_HOMO^b/eV	E_LUMO^c/eV	Eel g/eV
5a	495, 315, 293	2.25	590	390
5b	508, 335, 295	2.12	610	345	1.69	1.51	–1.13	–1.54	–0.98	–5.91	–3.42	2.49
5c	509, 335, 295	2.13	625	385	1.70	1.53	–1.12	–1.53	–0.95	–5.93	–3.45	2.48
5d	505, 335, 295	2.14	617	400	1.69	1.52	–1.13	–1.54	–0.98	–5.92	–3.42	2.50

Table 1. Optical data, decomposition temperatures and electrochemical properties for compounds 5a~5d

Figure 2. Normalized fluorescence spectra of 5a~5d (10 μmol/ L) recorded in DCM Excitation wavelength of 5a: 400 nm, excitation wavelength of 5b~5d: 450 nm, slit width 5 nm

Figure 3. Cyclic voltammograms of 5b~5d(0.001 mol /L)

Figure 4. Thermogravimetric analysis (TGA) plots of 5a~5d with a heating rate of 10 ℃?min–1 under N2

Figure 5. X-ray crystal structures of compounds (a) 5b and (b) 5c Red spheres depict O atoms and gray spheres C. Alkyl groups and hydrogen atoms have been omitted for clarity in packing.

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