Figure
4 The mechanism investigation of the photooxidation stability of SFDBA
crystal. The images of SFDBA crystal exposed to sunlight for different
time intervals: a) 0 h under optical microscope; b) 2 h, c) 4 h, and d)
8h under fluorescence microscope. e) The possible oxidation
intermediates and products during the self-sensitization process. f)
Schematic illustration of the encapsulation strategy.
4e demonstrates that the sunlight-sensitive naphthylamines are under the
protection of closely packed fluorenyl groups as a sterically hindered
“armor”, so that the oxygen molecules cannot invade into the largest
(100) plane but to attack the narrow
lateral face. Further, the calculated Fukui electrophilic functions of
the SFDBA molecule and its octamer indicate that the photooxidation
active site is located on the acridine ring of the SFDBA molecule and is
protected by the “armor” on the other side when the molecule
aggregates (Figure S6 & S7). The low-dimensional morphology restricts
the entrance of oxygen molecules, further minimizing the detrimental
effect of photooxidation.
Conclusions
In conclusion, a self-encapsulation strategy is displayed by utilizing
the ordered arranged stable part of the molecule to form an “armor”
for the effective protection of active fragments away from oxygen. The
molecular structure design, the molecular packing mode, and the
low-dimensional crystal morphology are mutually connected and work
together to promote the ultimate oxidative stability of SFDBA materials.
Experimental
Experimental Section. All of chemicals were purchased from J&K
Scientific Co. Ltd., and were used without further purification unless
otherwise stated.
Preparation of SFDBA
micro/nano-crystals. The microcrystals of SFDBA were fabricated through
reprecipitation method. Typically, 0.5 mg target compounds dissolved in
1 mL THF solution was injected into a 5 mL vigorously stirred water for
5 min, the sample was aging for about 24 h to stabilize the
nanostructures. Subsequently, the microcrystals underwent centrifugation
and were washed with pure water four times.
Preparation of SFDBA single crystals. Single crystals of
SFDBA were obtained by the
solvent diffusion methods, the growth conditions are manifested in Table
S1. Crystallographic information is summarized in Table S2 (these data
can also be obtained free of charge from the Cambridge Crystallographic
Data Centre: 794132 (SFDBA).
Preparation of SFDBA dilute solution. A certain mass of SFDBA
powder was added into 1 mL tetrahydrofuran solution to prepare a
solution with a concentration of 10-3 mol/L, and then
injected 30 μL the above solution into 3 mL tetrahydrofuran solution to
obtain a dilute solution with a concentration of 10-5mol/L.
Preparation of SFDBA amorphous film. A quartz sheet with a size
of 1.5*1.5 cm as the substrate was placed on the spin coater. The
tetrahydrofuran solution of the SFDBA with a concentration of 5 mg/mL
was dropped to the substrate. The spinning coating speed was 1200 rpm
for 30 s, and the acceleration was 400 rpm/s.
Characterization Details. 1H NMR spectra were
measured on a Varian Mercury Plus 400 spectrometer with
tetramethylsilane as the internal standard. For scanning electron
microscopic (SEM) studies, a drop of 15 μL target samples was
precipitated on the silicon substrates with the solvent completely
evaporated, and then the samples were examined with a field emission SEM
(Hitachi S-4800) at an accelerating voltage of 5 kV. The transmission
electron microscopy (TEM) and selected-area electron diffraction (SAED)
studies were performed in a JEM 2010F JEOL and operated at an
accelerating voltage of 100kV. The single crystal data collection was
performed at around 100 or 298 K on a Bruker 2000 CCD area detector
using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). All
structures were solved by direct methods using SHELXS-2015 and refined
against F2 using SHELXL-2015. X-ray diffraction (XRD) patterns were
performed on a Bruker D8 X-ray diffractometer with Cu KR radiation (λ =
1.54050 Å). The operating 2θ angle ranges from 5 to 30˚, with the step
length of 0.025˚. Photoluminescence (PL) emission spectra was measured
using a PerkinElmer LS55 spectrophotometer. Photoluminescence quantum
efficiency (PLQY) and fluorescence decay curves were measured using a
steady/transient fluorescence spectrometer (FLS 920). Fourier transform
infrared (FT-IR) spectra was obtained by a PerkinElmer Spectrum Two FTIR
spectrometer. The luminescence imaging was taken by Olympus IX71
inverted fluorescence microscope. All the theoretical calculations were
performed by using the B3LYP functional with the 6-31G(d) basis set
based on their crystallographic data.
Supporting Information
The supporting information for this article is available on the WWW
under https://doi.org/10.1002/cjoc.2023xxxxx.
Acknowledgement
This work was supported by the Funded by Natural Science Foundation of
Nanjing University of Posts and Telecommunications (NY222157, NY221085),
State Key Laboratory of Organic Electronics and Information Display
(GZR2022010008),Key Laboratory of Low-dimensional Materials Chemistry of
Jiangsu Province (JSKC20022), General Program of China Postdoctoral
Science Foundation (2022M711684), General Program of Basic Science
(Natural Science) of Colleges and Universities of Jiangsu Province
(22KJB430036), National Overseas Study Fund (202008320051), National Key
Laboratory (2009DS690095), and the National Natural Science Foundation
of China (62288102).
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