Perylene-3,4:9,10-tetracarboxylic Acid Bisimide Research Articles

Dictating Packing and Interactions of Perylene Bisimides within Cyclophane Structures in the Solid State

AbstractCrystal packing and chromophore communication are key parameters for the performance and functionality of many applications related to light‐energy harvesting and conversion. However, obtaining crystals of flexible and very soluble structures is troublesome. Nevertheless, a crystal structure of a highly flexible perylene‐3,4 : 9,10‐tetracarboxylic acid bisimide (PBI) cyclophane was obtained and analysed to compare the chromophore arrangement in the solid state with theconfiguration in solution as well as with calculated structures. The crystal structure exhibits an intra‐ and intermolecular slip‐stack arrangement of the heterochiral PBI units, forming a unique one‐dimensional π‐stacking supramolecular polymer‐like structure. These findings emphasize that the unique solid‐state arrangement of the chromophores cannot be easily predicted by elaborate studies in solution or by theoretical calculations. Furthermore, it features the importance of controlling the crystal packing to enable specific applications based on multiexciton generation processes where the spatial dependence and relative orientation of the chromophores are decisive parameters.

Bis-pseudorotaxane Formation of Perylene Bisimide-Linked [60]Fullerene Dumbbell-Like Molecules with [10]Cycloparaphenylene

Two [60]fullerene dumbbell-like molecules with a single or double perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI) linker were synthesized to study the structural and photophysical properties in addition to the complex formation with [10]cycloparaphenylene ([10]CPP). Due to their special optical properties, it is possible to describe the complexation using conventional spectroscopic methods such as NMR and fluorescence. However, isothermal titration calorimetry (ITC) was used to complete the analysis of the bis-pseudorotaxane formation by investigating the binding stoichiometries as well as the thermodynamic and kinetic parameters. It was observed that the PBI bridges do not inhibit the complexation with [10]CPP, giving rise to the formation of 1 : 1 and 1 : 2 complexes in o-dichlorobenzene with affinities of around 105 · M−1, similar to the [10]CPP⊃C60 reference system. A novel global analysis by combination of data sets from different techniques allowed us to follow the species distribution very precisely. ITC has proven to be a very powerful method for studying the complexation between fullerene derivatives and strained carbon nanohoops, which provides not only binding affinities and stoichiometries, but also all thermodynamic and kinetic parameters of the bis-pseudorotaxane formation. These results are of significant interest for the investigation of fullerene complexes in supramolecular chemistry and for their future applications in semiconductors and optoelectronics.

Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties

AbstractUnprecedented neutral perylene‐3,4:9,10‐tetracarboxylic acid bisimide (PBI) radicals and biradicals were synthesized by facile chemical oxidation of 4‐hydroxyaryl‐substituted PBIs. Subsequent characterization by optical and magnetic spectroscopic techniques, as well as quantum chemical calculations, revealed an open‐shell singlet biradical ground state for the PBI biradical OS‐2.. (〈s2〉=1.2191) with a relatively small singlet–triplet energy gap of 0.041 eV and a large singlet biradical character of y=0.72.

Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties.

Unprecedented neutral perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) radicals and biradicals were synthesized by facile chemical oxidation of 4-hydroxyaryl-substituted PBIs. Subsequent characterization by optical and magnetic spectroscopic techniques, as well as quantum chemical calculations, revealed an open-shell singlet biradical ground state for the PBI biradical OS-2(..) (〈s(2)〉=1.2191) with a relatively small singlet-triplet energy gap of 0.041 eV and a large singlet biradical character of y=0.72.

A Perylene Bisimide Cyclophane as a "Turn-On" and "Turn-Off" Fluorescence Probe.

A rigid, covalently linked perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) cyclophane was synthesized by imidization of a bay-substituted perylene bisanhydride with p-xylylenediamine. The interchromophoric distance of approximately 6.5 Å establishes an ideal rigid cavity for the encapsulation of large aromatic compounds such as perylene and anthracene with binding constants up to 4.6×10(4) M(-1) (in CHCl3 ). For electron-poor guest molecules, the complexation process is accompanied by a significantly increased fluorescence, whereas the emission intensity is dramatically quenched by more electron-rich guests because of the formation of charge-transfer complexes. Furthermore, the influence of the PBI core twist on the binding constant results in a remarkable selectivity towards more flexible aromatic guest molecules.

A Perylene Bisimide Cyclophane as a “Turn‐On” and “Turn‐Off” Fluorescence Probe

AbstractA rigid, covalently linked perylene‐3,4:9,10‐tetracarboxylic acid bisimide (PBI) cyclophane was synthesized by imidization of a bay‐substituted perylene bisanhydride with p‐xylylenediamine. The interchromophoric distance of approximately 6.5 Å establishes an ideal rigid cavity for the encapsulation of large aromatic compounds such as perylene and anthracene with binding constants up to 4.6×104 M−1 (in CHCl3). For electron‐poor guest molecules, the complexation process is accompanied by a significantly increased fluorescence, whereas the emission intensity is dramatically quenched by more electron‐rich guests because of the formation of charge‐transfer complexes. Furthermore, the influence of the PBI core twist on the binding constant results in a remarkable selectivity towards more flexible aromatic guest molecules.

Ambient stable zwitterionic perylene bisimide-centered radical.

The unexpected introduction of a cationic imidazolium substituent in the 2-position of a tetrachloro-substituted perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) by the reaction of PBI-Cl4 1 with the N-heterocyclic carbene 1,3-di-iso-propyl-imidazolin-2-ylidene ((i)Pr2Im 2) enables the isolation of an ambient stable zwitterionic radical. The remarkable stability of this unprecedented PBI-centered radical facilitates the complete characterization by several spectroscopic methods as well as single crystal structure analysis. Redox studies revealed that (i)Pr2Im-PBI-Cl4 4 can be transferred reversibly to the corresponding anion and cation, respectively, even on a preparative scale.

Ambient Stable Zwitterionic Perylene Bisimide‐Centered Radical

AbstractThe unexpected introduction of a cationic imidazolium substituent in the 2‐position of a tetrachloro‐substituted perylene‐3,4:9,10‐tetracarboxylic acid bisimide (PBI) by the reaction of PBI‐Cl4 1 with the N‐heterocyclic carbene 1,3‐di‐iso‐propyl‐imidazolin‐2‐ylidene (iPr2Im 2) enables the isolation of an ambient stable zwitterionic radical. The remarkable stability of this unprecedented PBI‐centered radical facilitates the complete characterization by several spectroscopic methods as well as single crystal structure analysis. Redox studies revealed that iPr2Im‐PBI‐Cl4 4 can be transferred reversibly to the corresponding anion and cation, respectively, even on a preparative scale.

Naked eye and fluorescent detections of Hg2+ ions and Cysteine via J-aggregation and deaggregation of a perylene bisimide derivative

Selective naked eye and fluorescent sensor responses of a 1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) derivative are reported for the first time toward Hg2+ ions and Cysteine (Cys) via J-aggregation and deaggregation mechanisms. The J-aggregation and deaggregation of PBI induced by Hg2+ and Cys were well established by UV–vis/PL and 1H NMR titrations. The 1:1 stoichiometry of PBI-Hg2+ and Cys-Hg2+/PBI ensembles were elucidated from the jobs plots based on their UV–vis spectral changes. The linear complex formation by PBI-Hg2+ ensemble was confirmed through FT-IR and 1H NMR spectral studies and well supported by its reversible nature upon the addition of pentamethyl diethylene triamine (PMDTA). The positive cooperativities of Hg2+ and Cys (with PBI) in PBI-Hg2+ and Cys-Hg2+/PBI ensembles were evidenced from the Hill plots based on their fluorescence binding isotherms. The detection limits of Hg2+ ions and Cys were calculated as 36.6 and 91.3nM, respectively, by standard deviations and linear fittings of their Stern–Volmer (KSV) constants and relative fluorescence intensity changes, respectively. Furthermore, the sensor properties of PBI were well investigated by KSV constants, pH values, time effects, and time resolved photoluminescence (TRPL) spectra.

Regioselective Photocyclization To Prepare Multifunctional Blocks for Ladder-Conjugated Materials

Multifunctional building blocks 8 and 9 were efficiently synthesized by fusing a perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI) core with o-phenylenediamine, and they were condensed with a pyrenedione and a pyrenetetraone, respectively, to construct new ladder-type conjugated oligomers 12 and 13. In the key photocyclization step, an unusual regioselectivity at the position ortho to the nitro group was discovered in the coupling of the o-nitroaniline functional units at the bay sites of PBI. Bulk-heterojunction solar cells based on 12 and 13 as the acceptors exhibited reasonable performance.

Transformation from Kinetically into Thermodynamically Controlled Self-Organization of Complex Helical Columns with 3D Periodicity Assembled from Dendronized Perylene Bisimides

The dendronized perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI), (3,4,5)12G1-1-PBI, was reported by our laboratory to self-assemble into complex helical columns containing dimers of dendronized PBI with one molecule in each stratum, with different intra- and interdimer rotation angles but identical intra- and interdimer distance of 3.5 Å, exhibiting a four-strata 2(1) helical repeat. A thermodynamically controlled 2D columnar hexagonal phase with short-range intracolumnar order represents the thermodynamic product at high temperature, while a kinetically controlled monoclinic columnar array with 3D periodicity is the thermodynamic product at low temperature. With heating and cooling rates higher than 10 °C/min to 1 °C/min, at low temperature the 2D columnar periodic array is the kinetic product for this dendronized PBI. Here the synthesis and structural analysis of a library of (3,4,5)nG1-m-PBI with n = 12 to 6 and m = 1 are reported. A combination of differential scanning calorimetry, X-ray diffraction on powder and orientated fibers, including pattern simulation and electron density map reconstruction, and solid-state NMR, all as a function of temperature and heating and cooling rate, was employed for their structural analysis. It was discovered that at low temperature the as-prepared n = 12 to 10 exhibit a 3D layered array that transforms irreversibly into columnar periodicities during heating and cooling. Also the kinetically controlled 3D columnar phase of n = 12 becomes thermodynamically controlled for n = 10, 9, 8, 7, and 6. This unprecedented transformation is expected to facilitate the design of functions from dendronized PBI and other self-assembling building blocks.

CO2-triggered fluorescence “turn-on” response of perylene diimide-containing poly(N,N-dimethylaminoethyl methacrylate)

A fluorophore–polymer conjugate, PBI–PDMAEMA, consisting of two arms of CO2-responsive N,N-dimethylaminoethyl methacrylate polymer (PDMAEMA) and a center perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI) fluorophore, has been synthesized via atom transfer radical polymerization of N,N-dimethylaminoethyl methacrylate from the N,N′-bis{2-[2-[(2-bromo-2-methylpropanoyl)oxy]ethoxy]ethyl}perylene-3,4,9,10-tetracarboxylic acid bisimide initiators. This fluorophore–polymer conjugate exhibits a colorimetric change and a fluorescent “turn-on” response to the presence of CO2 in aqueous solutions. Upon removal of adsorbed CO2 by N2 degassing, this CO2 chemosensor is completely recoverable. The application of this fluorophore–polymer conjugate in determining the concentration of CO2 in carbonated beverages was demonstrated.

Supramolecularly Engineered Perylene Bisimide Assemblies Exhibiting Thermal Transition from Columnar to Multilamellar Structures

Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substituents. The aggregation study in solution using UV-vis and NMR spectroscopies showed the formation of extended aggregates through hydrogen-bonding and π-π stacking interactions. The cylindrical fibrillar nanostructures were visualized by microscopic techniques (AFM, TEM), and the formation of lyotropic mesophase was confirmed by polarized optical microscopy and SEM. X-ray diffraction study revealed that a well-defined hexagonal columnar (Col(h)) structure was formed by solution-casting of fibrillar assemblies. All of these results are consistent with the formation of hydrogen-bonded PBI rosettes that spontaneously organize into the Col(h) structure. Upon heating the Col(h) structure in the bulk state, a structural transition to a highly ordered lamellar (Lam) structure was observed by variable-temperature X-ray diffraction, differential scanning calorimetry, and AFM studies. IR study showed that the rearrangement of the hydrogen-bonding motifs occurs during the structural transition. These results suggest that such a striking structural transition is aided by the reorganization in the lowest level of self-organization, i.e., the rearrangement of hydrogen-bonded motifs from rosette to linear tape. A remarkable increase in the transient photoconductivity was observed by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements upon converting the Col(h) structure to the Lam structure. Transient absorption spectroscopy revealed that electron transfer from electron-donating alkoxyphenyl groups of melamine components to electron-deficient PBI moieties takes place, resulting in a higher probability of charge carrier generation in the Lam structure compared to the Col(h) structure.

Self-Repairing Complex Helical Columns Generated via Kinetically Controlled Self-Assembly of Dendronized Perylene Bisimides

The dendronized perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI), (3,4,5)12G1-3-PBI, was recently reported to self-assemble in complex helical columns containing tetramers of PBI as basic repeat unit. These tetramers contain a pair of two molecules arranged side-by-side and another pair in the next stratum of the column turned upside-down and rotated around the column axis. Intra- and intertetramer rotation angles and stacking distances are different. At high temperature, (3,4,5)12G1-3-PBI self-assembles via a thermodynamically controlled process in a 2D hexagonal columnar phase while at low temperature in a 3D orthorhombic columnar array via a kinetically controlled process. Here, we report the synthesis and structural analysis, by a combination of differential scanning calorimetry, X-ray and electron diffraction, and solid-state NMR performed at different temperatures, on the supramolecular structures generated by a library of (3,4,5)nG1-3-PBI with n = 14-4. For n = 11-8, the kinetically controlled self-assembly from low temperature changes in a thermodynamically controlled process, while the orthorhombic columnar array for n = 9 and 8 transforms from the thermodynamic product into the kinetic product. The new thermodynamic product at low temperature for n = 9, 8 is a self-repaired helical column with an intra- and intertetramer distance of 3.5 Å forming a 3D monoclinic periodic array via a kinetically controlled self-assembly process. The complex dynamic process leading to this reorganization was elucidated by solid-state NMR and X-ray diffraction. This discovery is important for the field of self-assembly and for the molecular design of supramolecular electronics and solar cell.

A theoretical study of bipolar organic transport material: Disilanyl double-pillared bisanthracene (SiDPBA)

A novel anthracene derivative, disilanyl double-pillared bisanthracene (SiDPBA), has been recently synthesized, which effectively functions as a bipolar carrier transport material in OLEDs. Its charge transport properties have been systemically investigated by band model and hopping model. Band structure calculations of SiDPBA show that the dispersions of the larger valence band and conduction band are comparable, which demonstrates that both electron and hole are favoured for transport, and that SiDPBA has the potential to be used as bipolar transport material from the viewpoint of band model. The density of states and transfer integrals in the main pathways show that it is the edge-to-face CH···π interaction that determines the charge transport property, and that the SiMe2 group contibutes little to it. The calculated charge mobilities of holes and electrons are 0.461 and 0.116 cm2·V–1·s–1, respectively. They are the same order of magnitude, and the electron mobility is on the order of magnitude of perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) derivatives (0.34 cm2·V–1·s–1). Both models demonstrate that ·SiDPBA has the potential to be used as a bipolar transport material.

Water-soluble highly fluorescent poly[poly(ethylene glycol) methyl ether methacrylate] for cell labeling

A novel fluorescent brush-like poly[poly(ethylene glycol) methyl ether methacrylate] (P(PEGMA)) has been synthesized via facile atom transfer radical polymerization using perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI) as the initiator. The PBI–P(PEGMA) polymer has strong fluorescence in water and will be an effective bio-dye for cell labeling.