Fluorine interaction controlled AIEE phenomenon in an expanded calixbenzophyrin and its vapoluminescent response: turn on emission with volatile ketones and esters

Salini, P. S.; Holaday, M. G. Derry; Reddy, M. L. P.; Suresh, Cherumuttathu H.; Srinivasan, A.

doi:10.1039/c3cc38723b

Cited by 15 publications

(7 citation statements)

References 26 publications

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“…However, in 2 c , an interaction between the fluorine atom of the perfluorophenyl moiety and the methyl hydrogen (2.530 Å) was observed instead of the interaction between C‐6 of the indole moiety and a methylene hydrogen from the butyl group, as noted in 2 a . Notably, perfluorophenyl‐perfluorophenyl (π F ‐π F ) stacking between both blue and green molecules, and red and yellow molecules is observed, with a π F ‐π F stacking distance of 3.617 Å, which compares well with reported values (3.30–3.61 Å) [6b] …”

Section: Resultssupporting

confidence: 87%

Perfluorophenyl‐Perfluorophenyl Stacking‐Promoted Aggregation‐Induced Emission Enhancement of Crystalline 5‐Aryloxy‐3H‐Indole

et al. 2021

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Introduction of a perfluorophenyloxy group at the 5‐position of 3,3‐dibutyl‐2‐methyl‐3H‐indole efficiently promotes aggregation‐induced emission enhancement in both the crystalline solid‐state and in highly concentrated ethanolic solutions of the resultant analog. The phenomenon is attributed to aggregate formation, arising from perfluorophenyl‐perfluorophenyl stacking between the 3H‐indole units, the occurrence of which was deduced from single‐crystal X‐ray analysis of 3,3‐dibutyl‐5‐perfluorophenyloxy‐2‐methyl‐3H‐indole.

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Section: Resultssupporting

confidence: 87%

Perfluorophenyl‐Perfluorophenyl Stacking‐Promoted Aggregation‐Induced Emission Enhancement of Crystalline 5‐Aryloxy‐3H‐Indole

et al. 2021

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“…However, in recent years, a number of studies have shown that these type of interactions do exist and are not simply due to crystal packing. There are now a growing number of examples of F···F interactions being utilized as crystal engineering for applications in materials chemistry − or in catalysis …”

Section: Introductionmentioning

confidence: 99%

Further Evidence on the Importance of Fluorous–Fluorous Interactions in Supramolecular Chemistry: A Combined Structural and Computational Study

Omorodion

Twamley

Platts

et al. 2015

Crystal Growth & Design

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The solid-state structures of CF3(CF2)5CH2CO2H and a fluorous triazole are reported, both of which display a wide variety and large number of noncovalent interactions in their packing. The solid-state structure of CF3(CF2)5CH2CO2H is stabilized by multiple F···F contacts but only one C–H···F–C interaction, as well as O–H···O and C–H···O hydrogen bonds. In contrast to other reported structures, the torsion angles in the fluorous chain are close to 180°, which means that the fluorine atoms are eclipsed. A DFT study of the interactions in both compounds show that F···F interactions, along with stacking and C–H···F and C–H···O contacts, are individually weakly energetically stabilizing, but collectively, they can give rise to interaction energies of up to 13 kcal mol–1. A topological approach to the interactions using atoms-in-molecules (AIM) theory reveals that there are bond critical points between the C–F···F–C interactions as well as C–F···H–C interactions that are not recognized when using only the van der Waals distances.

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“…In this respect, uorination of A groups offers the possibility of modulating optical and electrical properties of push-pull organic chromophores, lowering their HOMO and LUMO energy levels and facilitating the charge transfer process, 3 thus enhancing the 2 nd order NLO response. 4 Fluorination also affects crystal packing of conjugated organic materials, 5 which is a key issue in determining their electronic and optical properties, 6 and therefore their potential use in electronic and optoelectronic devices. On the other hand, linear p-conjugated materials tend to strongly aggregate in the solid state and in concentrated solutions, yielding p-stacked structures, which oen suppress luminescence and NLO properties.…”

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confidence: 99%

Fluorine-induced J-aggregation enhances emissive properties of a new NLO push–pull chromophore

et al. 2014

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A new fluorinated push-pull chromophore with good second-order NLO properties even in concentrated solution shows solid state intermolecular aryl-fluoroaryl interactions leading to J-aggregates with intense solid state luminescence.Over the last few decades, organic-based optoelectronic materials displaying good 2 nd order nonlinear optical (NLO) and emission properties have received great scientic attention. 1Among all possible substrates, linear p-conjugated organic molecules, and notably p-phenylene vinylene (PPV) derivatives, are of particular interest due to their broad absorption bands, high luminescence quantum yields, and large Stokes shis. 2Moreover, PPV structures have been used as convenient pbridges between strong electron donor (D) and acceptor (A) groups, whose electronic properties can be nely tuned by the insertion of suitable electron-withdrawing or donating substituents. In this respect, uorination of A groups offers the possibility of modulating optical and electrical properties of push-pull organic chromophores, lowering their HOMO and LUMO energy levels and facilitating the charge transfer process, 3 thus enhancing the 2 nd order NLO response. 4 Fluorination also affects crystal packing of conjugated organic materials, 5 which is a key issue in determining their electronic and optical properties, 6 and therefore their potential use in electronic and optoelectronic devices. On the other hand, linear p-conjugated materials tend to strongly aggregate in the solid state and in concentrated solutions, yielding p-stacked structures, which oen suppress luminescence and NLO properties. A good strategy to optimize both properties is to design molecules characterized by a low tendency to aggregate when dispersed or dissolved, but selfassemble into J-type aggregates in the solid state. J-aggregates are characterized by a narrow and intense absorption band, bathochromically shied with respect to the isolated molecule, and are known to enhance both the emissive 8 and the NLO properties. 9Aryl-uoroaryl interactions, 10 among others, 11 have been exploited to dictate self-assembly of large aromatic chromophores into J-aggregates. 12,13We have recently reported the synthesis, structural, and optical characterization of a new NLO chromophore consisting of a push-pull system where a PPV moiety spaces an electrondonor end, working as the halogen-bond-acceptor terminus, and a p-iodotetrauorophenyl end, working as the halogenbond-donor terminus (1a in Scheme 1).14 This chromophore, while being effective from the point of view of NLO properties, did not show any emission in the solid state and a very low one in solution (Quantum Yield, QY ¼ 0.14 in toluene), as a likely consequence of the presence of iodine. Here our attention focuses on the de-iodinated derivative 1b (Scheme 1), which being devoid of the I atom, should not only be preserved from the heavy atom effect on luminescence, but also favor the aryluoroaryl interactions with respect to self-complementary halogen bonded arrangements. This, in fac...

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Fluorine interaction controlled AIEE phenomenon in an expanded calixbenzophyrin and its vapoluminescent response: turn on emission with volatile ketones and esters

Cited by 15 publications

References 26 publications

Perfluorophenyl‐Perfluorophenyl Stacking‐Promoted Aggregation‐Induced Emission Enhancement of Crystalline 5‐Aryloxy‐3H‐Indole

Perfluorophenyl‐Perfluorophenyl Stacking‐Promoted Aggregation‐Induced Emission Enhancement of Crystalline 5‐Aryloxy‐3H‐Indole

Further Evidence on the Importance of Fluorous–Fluorous Interactions in Supramolecular Chemistry: A Combined Structural and Computational Study

Fluorine-induced J-aggregation enhances emissive properties of a new NLO push–pull chromophore

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