Biomimetic molecular organization of naphthalene diimide in the solid state: tunable (chiro-) optical, viscoelastic and nanoscale properties

Makam, Pandeeswar; Khare, Harshavardhan; Ramakumar, Suryanarayanarao; Govindaraju, T.

doi:10.1039/c3ra47257d

Cited by 45 publications

(53 citation statements)

References 102 publications

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“…Such emissive soft matter materials have been highlighted for potential in drug delivery systems and bio‐sensing applications. Similar organogels are also observed using simple l ‐alanine and l ‐phenylalanine‐substituted NDIs to form blue/green to cyan‐emitting soft materials, attributed to the formation of solid‐state excimers and other π‐stack systems.…”

Section: Self‐assemblysupporting

confidence: 59%

“…When excited, the gels demonstrate emissive (l em,max 530 nm) behaviour with low,b ut observable F f of 0.04-0.05. [36] Such emissive soft matter materials have been highlighted for potential in drug delivery systems andb iosensing applications.S imilar organogels are also observed using simple l-alanine and l-phenylalanine-substituted NDIs to form blue/green to cyan-emitting soft materials, [37] attributed to the formationo fs olid-state excimers and other p-stack systems. [16].Copyright 2010 The Royal SocietyofC hemistry.g )Molecular structure of NDI-triazole cyclophane 37 and h) the mechanism of Mg 2 + sensing in NDI-triazole cyclophane 37.Reproduced with permission from Ref.…”

Section: Excimersmentioning

confidence: 94%

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Harnessing Brightness in Naphthalene Diimides

Maniam

Higginbotham

Bell

et al. 2019

Chemistry A European J

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The development of brightly emissive compounds is of great research and commercial interest, with established and emerging applications across chemistry, biology, physics, medicine and engineering. Among the many types of molecules available, naphthalene diimides have been widely used for both fundamental photophysical studies and in practical applications that utilise fluorescence as an information readout. The monomeric naphthalene diimide is weakly fluorescent, however through various methods of core‐derivatisation, it can be developed to be highly fluorescent and further functionalised to add utility. In this review, we highlight recent advances made in naphthalene diimide chemistry that have led to development of molecules with improved optical properties, and the design strategies utilised to produce bright fluorescence emission as small molecules or in supramolecular architectures.

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Section: Self‐assemblysupporting

confidence: 59%

Section: Excimersmentioning

confidence: 94%

Harnessing Brightness in Naphthalene Diimides

Maniam

Higginbotham

Bell

et al. 2019

Chemistry A European J

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“…[31][32][33][34][35] In this context, biomolecules such as amino acids and their derivatives are particularly appealing due to their remarkable metal chelating nature, aqueous solubility, specific molecular recognition, and ability to self-assemble into functional, complex and highly ordered molecular systems and nanomaterials through various noncovalent interactions. [36][37][38][39][40][41] Herein we report an easy and one step synthesis of PDI derivative 1 with L-DOPA functionality as a well-known receptor at the N-imide positions, and assembly-disassembly modulated detection of Fe 3+ and Cu 2+ metal ions. It was presumed that incorporation of L-DOPA would render the aqueous solubility to PDI derivative 1 and consequently a fluorescence probe in aqueous medium could be established.…”

Section: Introductionmentioning

confidence: 99%

Assembly Modulation of PDI Derivative as a Supramolecular Fluorescence Switching Probe for Detection of Cationic Surfactant and Metal Ions in Aqueous Media

Dwivedi

Makam

Govindaraju

2014

ACS Appl. Mater. Interfaces

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We report an amphiphilic perylene diimide (1), a bimolecular analog of l-3,4-dihydroxyphenylalanine (L-DOPA), as a reversible fluorescence switching probe for the detection and sensing of cationic surfactants and Fe(3+)/Cu(2+) in an aqueous media respectively by means of host-guest interactions driven assembly and disassembly of 1. Photophysical studies of 1, going from dimethyl sulfoxide (DMSO) (State-I) to pure aqueous medium (State-II), suggested the formation of self-assembled aggregates by displaying very weak fluorescence emission along with red shifted broad absorption bands. Interestingly, the cationic surfactant cetyltrimethylammonium bromide (CTAB) could disassemble 1 in miceller conditions by restoring bright yellow fluorescence and vibronically well-defined (Franck-Condon progressions A0-0/A0-1 ≈ 1.6) absorption bands of 1 over other neutral and anionic surfactants (State-III). Owing to the metal chelating nature of L-DOPA, 1 was able to sense Fe(3+) and Cu(2+) among a pool of other metal ions by means of fluorescence switching off state, attributed to metal interaction driven assembly of 1 (State-IV). Such metallosupramolecular assemblies were found to reverse back to the fluorescence switching on state using a metal ion chelator, diethylenetriaminepentaacetic acid (DTPA, State-III), further signifying the role of metal ions toward assembly of 1. Formation of assembly and disassembly could be visualized by the diminished and increased yellow emission under green laser light. Further, the assembly-disassembly modulation of 1 has been extensively characterized using infrared (IR), mass spectrometry, microscopy and dynamic light scattering (DLS) techniques. Therefore, modulation of the molecular self-assembly of PDI derivative 1 in aqueous media (assembled state, State-II) by means of host-guest interactions provided by micellar structures of CTAB (disassembled state, State-III), metal ion (Fe(3+) and Cu(2+)) interactions (assembled state, State-IV) and metal ion sequestration using DTPA (disassembled state, State-III) is viewed as a supramolecular reversible fluorescence switching off-on probe for cationic surfactant CTAB and Fe(3+)/Cu(2+).

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“…48 The combination of NDIs and siloxanes in discrete systems has already been investigated by others, 49−51 but none of these studies pushed the boundaries of molecular definition to an intermediate regime between small molecules and polymeric systems. The fully extended chemical structures of monodisperse Si15-NDI 2 -Si15 and NDI 2 -Si16-NDI 2 are shown in Chart 1 as examples.…”

mentioning

confidence: 99%

Unraveling the Driving Forces in the Self-Assembly of Monodisperse Naphthalenediimide-Oligodimethylsiloxane Block Molecules

et al. 2017

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Block molecules belong to a rapidly growing research field in materials chemistry in which discrete macromolecular architectures bridge the gap between block copolymers (BCP) and liquid crystals (LCs). The merging of characteristics from both BCP and LCs is expected to result in exciting breakthroughs, such as the discovery of unexpected morphologies or significant shrinking of domain spacings in materials that possess the high definition of organic molecules and the processability of polymers. Here we report the bulk self-assembly of two families of monodisperse block molecules comprised of naphthalenediimides (NDIs) and oligodimethylsiloxanes (ODMS). These materials are characterized by waxy texture, strong long-range order, and very low mobility, typical properties of conformationally disordered crystals. Our investigation unambiguously reveals that thermodynamic immiscibility and crystallization direct the self-assembly of ODMS-based block molecules. We show that a synergy of high incompatibility between the blocks and crystallization of the NDIs causes nanophase separation, giving access to hexagonally packed columnar (Colh) and lamellar (LAM) morphologies with sub-10 nm periodicities. The domain spacings can be tuned by mixing molecules with different ODMS lengths and the same number of NDIs, introducing an additional layer of control. X-ray scattering experiments reveal macrophase separation whenever this constitutional bias is not observed. Finally, we highlight our “ingredient approach” to obtain perfect order in sub-10 nm structured materials with a simple strategy built on a crystalline “hard” moiety and an incompatible “soft” ODMS partner. Following this simple rule, our recipe can be extended to a number of systems.

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Biomimetic molecular organization of naphthalene diimide in the solid state: tunable (chiro-) optical, viscoelastic and nanoscale properties

Abstract: Biomimetic molecular organization of naphthalene diimide in the solid state: tunable (chiro-) optical, viscoelastic and nanoscale properties.

Cited by 45 publications

References 102 publications

Harnessing Brightness in Naphthalene Diimides

Harnessing Brightness in Naphthalene Diimides

Assembly Modulation of PDI Derivative as a Supramolecular Fluorescence Switching Probe for Detection of Cationic Surfactant and Metal Ions in Aqueous Media

Unraveling the Driving Forces in the Self-Assembly of Monodisperse Naphthalenediimide-Oligodimethylsiloxane Block Molecules

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