Chemistry - A European Journal
10.1002/chem.202102296
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derivatives. Specifically, emission maxima at 453−487 nm, with
quantum yields in the range of 4.6%−14% were seen. We expect
that fluorescent SOFs, such as those detailed here, that combine
the fluorescent features of AIEs with porous structures, could be
useful in terms of preparing stimuli-responsive luminescent
materials.
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Experimental Section
Full details of the synthesis and characterisation of mono-amidine
substituted TPE-Amidine can be found in the Supporting Information. X-
ray crystallographic coordinates for the structures reported in this study have been
deposited at the Cambridge Crystallographic Data Centre (CCDC) under
deposition numbers 2056896, 2056901, 2056902, 2056903, and 2056904.
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Synthesis of 4,4',4'',4'''-(ethene-1,1,2,2-tetrayl)tetrabenzimidamide
tetrahydrochloride (TPE·4HCl).
Tetra(4-cyanophenyl)ethylene (0.8 g, 1.85 mmol) was dissolved in dry THF
[
8]
(
60 mL) at -40 °C under a nitrogen atmosphere, and LiHMDS solution (1.0
M in THF, 37 mL, 37 mmol) was added dropwise. The mixture was allowed
to warm to room temperature and stirred overnight. The reaction mixture
was cooled to 0 °C and ethanolic HCl (prepared by cautiously adding 10
mL of acetyl chloride to 100 mL ethanol) was added slowly, which resulted
in the formation of a pale precipitate. The precipitate was isolated by
centrifugation, and then suspended in ethanol (10 mL) and sonicated for 1
hour. The solid was again isolated by centrifugation, washed thoroughly
with ethanol and dried in vacuo to give TPE·4HCl (0.78 g, 65%) as a pale
1
0006−10012.
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1
solid. H NMR (400 MHz, D2O) δH: 7.44 (8H, d, J = 8.24 Hz), 7.21 (8H, d,
1
J = 8.24 Hz). H NMR (400 MHz, DMSO-d6) δH: 9.32 (8H, s), 9.04 (8H, s),
10]
7
.69 (8H, d, J = 8.4 Hz), 7.26 (8H, d, J = 8.4 Hz). 13C NMR (100 MHz, D2O)
δC: 166.1, 147.4, 141.6, 131.9, 127.6, 126.6. MS ESI-MS calcd for
[
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11] H. J. Barber, R. Slack, J. Chem. Soc. 1947, 82-84.
+
C30H29N8 [M – 4HCl + H ] 501.25, found 501.2; C30H29N8Na [M – 4HCl +
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+
+
Na] 523.23, found 523.2; C30H30N8 [M – 4HCl + 2H] 251.63, found 251.2.
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H. Wang is grateful for support from the National Natural Science
Foundation of China (21975153) and the Shanghai Pujiang
Program (2019PJD017). Q. H. thanks the Science Technology
Plan Project of Hunan Province, China (grant number
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019RS1018 to Q. H.), and Fundamental Research Funds for the
Central Universities (Startup Funds to Q. H.) for project funding.
J. Sessler acknowledges the Robert A. Welch Foundation (F-
0
018) for financial support.
Keywords: supramolecular organic frameworks • amidinium-
carboxylate salt bridge • self-assembly • aggregation-induced
emission • fluorescence
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