Cocrystals of 10-Methylphenthiazine and 1,3-Dinitrobenzene: Implications for the Optical Sensing of TNT-Based Explosives

Mcneil, Steven Keith; Kelley, Steven P.; Beg, Cameran; Cook, Hamilton; Rogers, Robin D.; Nikles, David E.

doi:10.1021/am401961s

Cited by 24 publications

(23 citation statements)

References 23 publications

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“…Fluorescence properties of organic compounds rely not only on the structure of the fluorophore but also on the architecture of crystal packing and simultaneously on the nature and strength of intermolecular interactions . Organic compounds with molecular-packing-directed luminescence , have gained significant popularity and attention due to their remarkable properties and promising optoelectronic applications in the fields of lasers, sensors, organic light-emitting diodes,and optical data storage . Numerous strategies have been employed to acquire tunable luminescent materials, since traditional structure tailoring techniques on single molecular materials have accomplished restricted success.…”

Section: Introductionmentioning

confidence: 99%

“…It has been generally found that π-conjugated organic molecules consisting of electron-donating or -withdrawing substituents have the usual propensity to co-crystallize through π–π stacking interactions in two different packing motifs, namely, segregated stacking , and mixed stacking . In the segregated stacking mode, the π-electron-rich (A) and π-electron-deficient (B) molecules form separate π-stacked columns (A–A–A–A, B–B–B–B), whereas in the mixed stacking mode, the constituent molecules are alternately arranged over each other along the π-stacking column (A–B–A–B).…”

Section: Introductionmentioning

confidence: 99%

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Exploring the Relationship between Intermolecular Interactions and Solid-State Photophysical Properties of Organic Co-Crystals

et al. 2018

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Five new binary co-crystals have been prepared through molecular self-assembly of π-electron-rich molecules, such as phenanthrene, benzo[c]cinnoline, and phenazine, in the presence of π-electron-deficient molecules, such as tetrafluoro-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, and 1,2,4,5-tetracyanobenzene, taken in an equimolar ratio. Crystal structure analysis revealed that in three binary co-crystals the constituent molecules were alternately sandwiched in a cofacial arrangement through π•••π interactions, whereas in the remaining two binary co-crystals the constituent molecules were aligned in a unique edge-to-face manner through lp•••π interactions. Co-crystals with π-stacking arrangement were fluorescent, whereas almost complete quenching of luminescence was observed in those having edge-to-face alignment of molecules. The photophysical observations of these co-crystals have been demonstrated via energetic quantification of the intermolecular interaction topology, which provides a molecular level understanding of factors controlling their solid-state absorption and luminescence behavior.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Exploring the Relationship between Intermolecular Interactions and Solid-State Photophysical Properties of Organic Co-Crystals

et al. 2018

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“…1,2 Several methods are used to detect those explosives like surface plasma resonance, field effect transition, portable mass spectrometry, ion mobility spectrometry, Xray systems, electrochemical methods, microcantilever and optical based sensing. [3][4][5][6][7] Among them, fluorescence based optical sensing is one of the finest techniques to detect those nitro explosives and become very popular because of its simple instrumentation, cost-efficiency, fast and high sensitivity. 8,9 Generally, nitro-aromatic derivatives are being used world-wide to prepare different explosives.…”

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confidence: 99%

Highly Selective Detection of Trinitrophenol by Luminescent Functionalized Reduced Graphene Oxide through FRET Mechanism

Dinda

Gupta

Shaw

et al. 2014

ACS Appl. Mater. Interfaces

188

100

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Among different nitro compounds, trinitrophenol (TNP) is the most common constituent to prepare powerful explosives all over the world. A few works on the detection of nitro explosives have already been reported in the past few years; however, selectivity is still in its infant stage. As all the nitroexplosives are highly electron deficient in nature, it is very difficult to separate one from a mixture of different nitro compounds by the usual photoinduced electron transfer (PET) mechanism. In the present work, we have used a bright luminescent, 2,6-diamino pyridine functionalized graphene oxide (DAP-RGO) for selective detection of TNP in the presence of other nitro compounds. The major advantage of using this material over other reported materials is not only to achieve very high fluorescence quenching of ∼96% but also superior selectivity >80% in the detection of TNP in aqueous medium via both fluorescence resonance energy transfer and PET mechanisms. Density functional theory calculations also suggest the occurrence of an effective proton transfer mechanism from TNP to DAP-RGO, resulting in this tremendous fluorescence quenching compared to other nitro compounds. We believe this graphene based composite will emerge a new class of materials that could be potentially useful for selective detection, even for trace amounts of nitro explosives in water.

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“…Our group and others have reported recently the significance and ability of luminescent coordination polymers , and metal organic frameworks in the detection of nitro-aromatics. It is known that the nitro-aromatics are electron-deficient compounds and able to form colored CT complexes with electron-rich compounds. , However, the excited state behavior, in particular, the ISC between singlet and triplet state of CT cocrystals, formed by the combination of nitro-aromatics and electron rich compounds is limited in the literature.…”

Section: Introductionmentioning

confidence: 99%

“…It is known that the nitro-aromatics are electron-deficient compounds and able to form colored CT complexes with electron-rich compounds. 33,34 However, the excited state behavior, in particular, the ISC between singlet and triplet state of CT cocrystals, formed by the combination of nitro-aromatics and electron rich compounds is limited in the literature.…”

Section: ■ Introductionmentioning

confidence: 99%

Effect of Noncovalent Interactions on the Intersystem Crossing Behavior in Charge-Transfer Cocrystals of 3,5-Dinitrobromobenzene

Gude

Biradha

2020

J. Phys. Chem. C

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The strength of the noncovalent interactions between donor and acceptor in charge-transfer (CT) cocrystals plays a significant role in controlling their optical behavior. Herein, we demonstrate the predominant influence of CT interactions between polarized π-systems on the intersystem crossing (ISC) between singlet and triplet states of three organic cocrystals. The cocrystals 1–3 are formed by the combination of an electron-deficient molecule such as 3,5-dintrobromobenzene (DNBB) with electron-rich molecules such as 4,4′-bipyridylethylene, carbazole, and 3,6-dibromocarbazole, respectively. The DNBB found to favor C–H···X hydrogen bonds over halogen bonds (Br···X) which was rationalized through electrostatic potential (ESP) of atomic sites of the molecules. The crystal structure analyses of cocrystals reveal that 1 exhibits infinite segregated stacks (−D–D–D– and −A–A–A−) and discrete mixed stacks (A–D–D–A) of donors and acceptors. On the other hand, 2 exhibits infinite mixed stacks (−D–A–D–A−) and 3 exhibits an offset fashion of infinite mixed stacks (−D–A–D–A−) of donors and acceptors, respectively. The predominant CT-stacking interactions affected the nature of electronic transitions and eventually the rate of ISC followed by phosphorescence behavior of cocrystals. The DNBB and cocrystal 1 found to exhibit phosphorescence but not 2 and 3. The optical behavior of DNBB and its binary cocrystals was rationalized by the time-dependent density functional theory (TDDFT) studies, spin–orbit coupling constant, and observed stacking interactions in the crystals. This work demonstrates the significance of nitro-aromatics in the design of solid state organic phosphorescent materials.

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Cocrystals of 10-Methylphenthiazine and 1,3-Dinitrobenzene: Implications for the Optical Sensing of TNT-Based Explosives

Cited by 24 publications

References 23 publications

Exploring the Relationship between Intermolecular Interactions and Solid-State Photophysical Properties of Organic Co-Crystals

Exploring the Relationship between Intermolecular Interactions and Solid-State Photophysical Properties of Organic Co-Crystals

Highly Selective Detection of Trinitrophenol by Luminescent Functionalized Reduced Graphene Oxide through FRET Mechanism

Effect of Noncovalent Interactions on the Intersystem Crossing Behavior in Charge-Transfer Cocrystals of 3,5-Dinitrobromobenzene

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