Novel EDTA-ligands containing an integral perylene bisimide (PBI) core as an optical reporter unit

Abstract

The synthesis, characterization and metal complexation of a new class of perylene bisimides (PBIs) as an integral part of ethylenediaminetetraacetic acid (EDTA) are reported. The simplest representative, namely derivative 1a, was synthesized both by a convergent as well as a direct approach while the elongated derivatives, 1b and 1c, were obtained only via a convergent synthetic pathway. All these new prototypes of water-soluble perylenes are bolaamphiphiles and were fully characterized by 1 H-and 13 C-NMR spectroscopy, matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry and IR spectroscopy. In order to acquaint ourselves with the behaviour in solution of our PBIs bearing dendritic wedges, the simplest derivative, 1a, was chosen and tested by means of UV/Vis and fluorescence spectroscopy as well as by zeta-potential measurements. A photoexcitation induced intramolecular photo-electron transfer (PET) can be observed in these molecules. Therefore their potential applications as sensors can be imagined. Model compound 1a efficiently coordinates trivalent metal cations both in water and dimethyl sulfoxide (DMSO). Significantly, the effects of the complexation strongly depend on the aggregation state of the PBI molecules in solution. As a matter of fact, in water, the presence of M 3+ ions triggers the formation of light emitting supramolecular aggregates (excimers). On the other hand, in DMSO-rich solutions metal complexation leads to the suppression of the PET and leads to a strong fluorescence enhancement.

Ionic Self‐Assembled Platform of Perylenediimide–Sodium Dodecylsulfate for Detection of Spermine in Clinical Samples

“…In continuation of our interesti nf unctionalized PDIs [12][13][14] and self-assembled supramolecular nanostructures, [32][33][34] herein we employ aw ater-soluble cationic perylenediimide derivative (N 1 -dodecyl-N 3 -(4-phenyl)benzimidazolium-functionalized perylenediimide (DAB-PDI)) to construct as imple,f ast, and sensitive ensemble (DAB-PDI-SDS) for the fluorescencet urn-on detection of spermine in water,u rine, and blood serum. Scheme 1d epictst he rationale for the assay strategy.T he DAB-PDI derivativeiss trongly fluorescent (F = 0.55) and forms nanoaggregates with diameters of 40-80 nm in a1 :1 mixture of H 2 O/CH 3 CN.…”

“…Perylene diimides( PDIs),w hich form an interesting class of functional organicd yes, have been used as high-performance pigments, [10,11] supramolecularh osts, [12][13][14][15][16][17] and in optoelectronic devices. [18,19] The functionalization of PDIs at bay-, peri-, ortho-, and N-terminal positions is being performed to increaset he solubility of PDIs in organic solvents.…”

Self-Assembled Fluorescent Nanoparticles from π-Conjugated Small Molecules: En Route to Biological Applications

“…2015, 36, 1306−1321 Figure 14. Charged ionic bolaamphiphilic PBI 35 , 36 , 37 and 38 by Sun et al, [ 114 ] Würthner et al, [ 115 ] Liu et al [ 116 ] and Hirsch et al, [ 120 ] respectively, which are able to aggregate into rod-like structures. Figure 13.…”

Nanomolar Cu2+Detection in Water Based on Disassembly of AIEgen: Applications in Blood Serum, Cell Imaging and Complex Logic Circuits

“…Recently, we reported assembly‐disassembly driven selective and sensitive detection of Cu 2+ , Pd 0 /Pd 2+ , ClO 4 − and picric acid . In continuation of our interest in assembly‐disassembly based chemosensing probes, herein, we report disassembly based AIEgen 1 for the detection of Cu 2+ in water, blood serum and complicated environmental (tap, pond and industrial waste water) samples.…”

“…[41][42][43] Recently, we reported assembly-disassembly driven selective and sensitive detection of Cu 2 + , Pd 0 /Pd 2 + , ClO 4 À and picric acid. [44][45][46][47][48][49][50][51][52][53][54] In continuation of our interest in assembly-disassembly based chemosensing probes, herein, we report disassembly based AIEgen 1 for the detection of Cu 2 + in water, blood serum and complicated environmental (tap, pond and industrial waste water) samples. The limit of detection is 0.261 ppb (4.13 nM) and is significantly lower than reported for any other AIEgen based sensor.…”