Rational design of a pyrene based luminescent porous supramolecular framework: excimer emission and energy transfer

Prasad, Komal; Haldar, Ritesh; Maji, Tapas Kumar

doi:10.1039/c5ra14267a

Cited by 16 publications

(8 citation statements)

References 43 publications

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“…Then the complex was reacted with ATP and ADP in THF/water, and after the solvent was removed with the vacuum, the prepared compound was washed with water, to remove the free phosphate species. The broad XRD pattern of R3 –ATP revealed the formation of polymeric aggregates, whereas solid state XRD spectra of R3 -ADP showed sharp peaks, which also have similarity with XRD spectra of R3 complex. To confirm the formation of the R3 –ATP complex, Raman spectra were recorded.…”

Section: Resultsmentioning

confidence: 55%

ATP Induced Modulation in π–π Stacking Interactions in Pyrene Based Zinc Complexes: Chemosensor Study and Quantitative Investigation of Apyrase Activity

Singh

Raj

Dubowski

et al. 2018

Crystal Growth & Design

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Fluorescent zinc complexes of 1,2-disubstituted benzimidazole (R1–R3) have been synthesized and characterized using single crystal X-ray diffraction. The ligands L1–3 were found to be less emissive due to photoinduced electron transfer (PET) mechanism originated from the electron pair of benzimidazole nitrogen. The complexation of ligands with Zn(II) not only enhances the fluorescent intensity; it also orients the ligands to a new packing. It was observed that the aromatic unit plays a decisive role in the packing of the molecules. The complex R1 has extended the coordination through C–H···π interaction, whereas complex R2 involved C–H···π interaction and C–H···Br interaction for packing in supramolecular architecture. Among these complexes, R3 showed the most interesting noncovalent interaction pattern involving C–H···π interaction, C–H···Br interaction, and π–π stacking between pyrene rings. These noncovalent interactions govern photophysical properties that are sensitive toward the microenvironment. Thus, by altering these interactions, the selective sensing for a particular analyte can be achieved. The complexes R1 and R2 have shown enhanced emission intensity upon interacting with adenosine triphosphate (ATP) competitively in the presence of some other tested anions. A ratiometric change in emission spectra of the complex R3 was observed upon binding with ATP in semiaqueous medium offering the lowest detection limit of 15 nM. Upon interaction with ATP, the π–π stacking between pyrene rings breaks and results in a decrease in excimer emission at 470 nm and increases in monomeric emission intensity at 410 nm. The AFM (Atomic force microscopy) images of receptor R3 show that upon addition of ATP to the R3 solution, solvent mediated aggregation takes place, which results in the ratiometric detection. In the dimethylformamide solvent system, aggregates were formed, whereas in a water/tetrahydrofuran solvent system the clear solution was converted to a highly viscous gel. To investigate the applications of the prepared sensor, the fluorescence response of HeLa cells enriched with ATP was observed using fluorescence microscopy. The fluorescence modulation of the sensor in living cells makes the receptor practically applicable in a biological environment. Quantitative analysis of apyrase activity has shown that the presented sensor R3 is capable of monitoring the hydrolysis process in the biological system.

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Section: Resultsmentioning

confidence: 55%

ATP Induced Modulation in π–π Stacking Interactions in Pyrene Based Zinc Complexes: Chemosensor Study and Quantitative Investigation of Apyrase Activity

Singh

Raj

Dubowski

et al. 2018

Crystal Growth & Design

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“…To ensure a correct interpretation, its origin can be further clarified by examining the distance between the packing units and the alignment of transition dipole moments in the crystal structures. It is well known that the optimum intermolecular distance for the excitonic coupling is about 3–4 Å for many organic molecules . However, regarding Si‐ m ‐Cb , the observed distances between two neighboring units are 10.66 Å (for face‐to‐face interactions) and 13.88 Å (for head‐to‐tail interaction; see Figure S10 in the Supporting Information).…”

Section: Discussionmentioning

confidence: 98%

“…It is well known that the optimum intermolecular distance for the excitonic coupling is about3-4 for many organic molecules. [58][59][60] However,r egarding Si-m-Cb,t he observed distances betweent wo neighboring units are 10.66 (for face-to-face interactions) and 13.88 (for head-to-tail interaction;s ee Figure S10 in the Supporting Information). As the dipole-dipolee xcitonici nteraction energy is inverselyp roportional to r 3 ,w here r denotes the distance between two transition dipoles, these values are too large to lead to redshifted emission by strong excitonic splitting.…”

Section: Discussionmentioning

confidence: 99%

Solid‐State Photochromism by Molecular Assembly of Bis‐o‐carboranyl Siloles

Cho

Kim

Lee

et al. 2019

Chemistry A European J

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A new type of solid‐state photochromism was observed in an AB2‐type molecular assembly comprising a central silole and two peripheral o‐carborane units, and in this assembly, depending on the assembling positions of those units at the adjoining benzene ring, two different regioisomers were formed: Si‐m‐Cb and Si‐p‐Cb. Each isomer showed different solid‐state photochromism depending on its solid‐state molecular conformation and was either in the crystalline or amorphous state. The crystals of each meta‐ or para‐isomer, CSi‐m‐Cb or CSi‐p‐Cb, showed yellow or blue emission, and mechanically grinding those crystals into amorphous powders of ASi‐m‐Cb and ASi‐p‐Cb, switched their emissions to blue and yellow, respectively. Photophysical studies revealed that the electronic interaction between silole and o‐carborane units determined the emission color. The crystal and DFT‐optimized structures each account for the crystalline and amorphous structures, respectively, and are correlated well with the electronic interactions in the molecular assembly in the solid state, thus enabling the prediction of the solid‐state molecular conformational change.

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“…Coordination complexes are widely used as efficient light-harvesting materials because they can hold chromophores in close proximity inside the lattice with the highest degree of order. − ,− Moreover, coordination-driven spatial organization of multichromophoric ligands results in novel photophysical properties in coordination complexes . For example, coordination complexes, synthesized by combining electron-rich and -deficient chromophoric ligands, often produce donor–acceptor or charge-transfer (CT) complexes with exciting properties like exciplex or CT emission. − Moreover, in a few cases, excitation energy-transfer phenomena were also observed from a neighboring chromophore to the exciplex or CT complex, leading to an enhanced and tunable emissive material. , Significant spectral overlap between the donor emission and acceptor absorbance as well as an optimum donor–acceptor distance are the primary requirements to realize the energy-transfer process. Such materials provide the additional advantage of absorbing light from a wider spectral range.…”

mentioning

confidence: 99%

Excitation Energy Transfer Supported Amplified Charge-Transfer Emission in an Anthracenedicarboxylate- and Bipyridophenazine-Based Coordination Complex

et al. 2018

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A highly luminescent tetrameric zinc(II) complex, {[Zn(adc)(bpz)(HCOO)]·2HO} (1; adc = 9,10-anthracenedicarboxylate and bpz = bipyridophenazine), was synthesized by a solvothermal technique and characterized by single-crystal X-ray diffraction. The linear tetrameric units extend into three dimensions via π stacking of adc/bpz and bpz/bpz and multiple CH-π interactions. The compound shows strong red emission at 597 nm (λ = 480 nm), which is attributed to charge-transfer (CT) emission within an adc/bpz donor-acceptor pair. This is also supported by density functional theory computations. Interestingly, the CT emission is amplified by energy transfer from another adc linker that is not involved in the CT interaction.

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Rational design of a pyrene based luminescent porous supramolecular framework: excimer emission and energy transfer

Abstract: Based on rational design and synthesis approach, a pyrene based supramolecular flexible porous framework of Zn(ii) has been synthesized. It shows excimer emission and has been exploited for light harvesting application.

Cited by 16 publications

References 43 publications

ATP Induced Modulation in π–π Stacking Interactions in Pyrene Based Zinc Complexes: Chemosensor Study and Quantitative Investigation of Apyrase Activity

ATP Induced Modulation in π–π Stacking Interactions in Pyrene Based Zinc Complexes: Chemosensor Study and Quantitative Investigation of Apyrase Activity

Solid‐State Photochromism by Molecular Assembly of Bis‐o‐carboranyl Siloles

Excitation Energy Transfer Supported Amplified Charge-Transfer Emission in an Anthracenedicarboxylate- and Bipyridophenazine-Based Coordination Complex

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