Folding of a Donor‐Containing Ionene by Intercalation with an Acceptor

Abstract

Cationic ionenes that bear electron-rich 1,5-dialkoxynaphthalene (DAN) units within the alkylene segment were allowed to interact with different types of electron-deficient, acceptor-containing molecules in an effort to realize intercalation-induced folding of the ionenes; the collapse of the chains was expected to occur in such a way that the donor and acceptor units become arranged in an alternating fashion. Several acceptor-bearing molecules were prepared by the derivatization of pyromellitic dianhydride and naphthalene tetracarboxylic dianhydride with two different oligoethylene glycol monomethyl ether monoamines. This yielded acceptor molecules with different water solubility and allowed the examination of solvophobic effects in the folding process. UV/Vis spectroscopic studies were carried out by using a 1:1 mixture of the DAN-ionenes and different acceptor molecules in water/DMSO solvent mixtures. The intensity of the charge-transfer (CT) band was seen to increase with the water content in the solvent mixture, thereby suggesting that the intercalation is indeed aided by solvophobic effects. The naphthalene diimide (NDI) bearing acceptor molecules consistently formed significantly stronger CT complexes when compared to the pyromellitic diimide (PDI) bearing acceptor molecules, which is a reflection of the stronger π-stacking tendency of the former. AFM studies of drop-cast films of different ionene-acceptor combinations revealed that compact folded structures are formed most effectively under conditions in which the strongest CT complex is formed.

Hydrogen‐Bonding‐Mediated J‐Aggregation and White‐Light Emission from a Remarkably Simple, Single‐Component, Naphthalenediimide Chromophore

“…In this mode the carboxylic acid groups are involved in hydrogen bonding with varying strength, as suggested by slightly different length for hydrogen bonds (shown in Figure 3 a), and also the two adjacent NDI chromophores are located within p-stacking distance, as observed in the crystal structure of NDI chromophore. [17] It is also worth noting that in the proposed packing model, the chromophores are stacked with significant longitudinal displacement along the long axis of the NDI chromophores, which corroborates well with the prominent aggregation-induced redshift in the absorption spectra.…”

“…In the recent past, we have been engaged in understanding effect of structural variations on hydrogen-bonding mediated self-assembly of 1,4,5,8-naphthalenetetracarboxdi-A C H T U N G T R E N N U N G imide (NDI) derivatives [8] due to the prospect of using this particular chromophore [9] as an n-type semiconductor. [10] NDI derivatives have also been extensively utilized as building blocks for various elegant supramolecular materials, such as synthetic ion channels, [11] organogels, [8,12] hydrogels, [13] nanotubes, [6,14] catenanes, [15] rotaxanes, [16] foldamers, [17] supramolecular photosystems, [18] nanoparticles, [19] and other amphiphilic nanostructures. [20] As a part of our continuing interest in self-assembly of NDI chromophore, we synthesized NDI-1 (Figure 1), which contains a carboxylic acid group that is capable of forming a self-complementary hydrogen-bonding network and a dodecyl chain to provide enhanced solubility in relatively nonpolar solvents.…”

Selective Detection of Hg2+ Ions with Boron Dipyrromethene‐Based Fluorescent Probes Appended with a Bis(1,2,3‐triazole)amino Receptor

“…All other solvents and reagents were of analytical grade and used as received. Compounds 1 , 4 , and 7 were prepared as described.…”

“…All other solvents and reagents were of analytical grade and used as received. Compounds 1, [9] 4, [10] and 7 [11] were prepared as described. 1 Ha nd 13 C{ 1 H} NMR spectra were recorded on aB ruker AVANCE III 400 spectrometer ( 1 H, 400 MHz; 13 resonances relative to SiMe 4 .E SI mass spectra were recorded on a Thermo Finnigan MAT9 5X Lm ass spectrometer.E lemental analyses were performed by the Shanghai Institute of Organic Chemistry,C hinese Academy of Sciences, China.…”

Effect of Amide Hydrogen Bonding Interaction on Supramolecular Self‐Assembly of Naphthalene Diimide Amphiphiles with Aggregation Induced Emission

“…[4] Naphthalene diimide (NDI) chromophores [5] have drawn considerable attentiond ue to their unique optical and electronic properties, which have led to various applicationsi ns ensors, [4] semicon-ductor devices, [2b, 6] organic phtovoltaic devices, [7] and artificial photosynthesis, [8] as well as biological applications. [9] Furthermore, NDI derivatives have been extensively investigated in the field of supramolecular self-assembly to produce well-defined nanostructures such as nanobelts, [10] nanotubes, [2f, 11] ion channels, [12] hydrogels, [13] organogels, [14] catenanes, [15] rotaxanes, [16] foldamers, [17] nanoparticles, [18] stimuli responsive nanomaterials, [19] and aggregation-induced emission enhancement (AIEE) [20] nanostructures.…”