Amino Acid Derivatized Arylenediimides: A Versatile Modular Approach for Functional Molecular Materials

Avinash, M. B.; Govindaraju, T.

doi:10.1002/adma.201201544

Cited by 96 publications

(68 citation statements)

References 98 publications

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“…[1][2][3][4][5][6][7] With such advantageous properties, PDI derivatives have been considered as optimal fluorescent dyes and utilized in a wide variety of applications such as laser dyes, photovoltaic cells, fluorescence switches, molecular wires, molecular transistors and sensors. [8][9][10][11][12][13][14][15][16][17] However, PDI structure and planar π-electron deficient aromatic nature are known to promote strongly the formation of aggregates through stacking interactions between the π-conjugated core 1 and this strong aggregation tendency in aqueous media results in fluorescence quenching.…”

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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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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“…Thus, to extend the envisioned ordering from the molecular level to well‐defined supramolecular architectures on a microscopic scale and also to explore systematic molecular structural mutation induced structure–property correlations, we have designed amino acid functionalized dyads of NDI and pyrene ( 1 – 5 ). The amino acid auxiliaries for tailoring the molecular assemblies were chosen on the basis of the phenomenal molecular/chiral recognition and distinctive sequence‐specific self‐assembling properties embodied in them as a result of over a billion years of stringent natural selection 1e. Specifically, by introducing minute molecular structural mutations in the side‐chain of the amino acid auxiliary (Figure 1), striking variations in the supramolecular architectures, namely supercoiled helices, twisted nanoribbons, nanobelts, comb‐edged nanoflakes and nanosheets, were realized.…”

Section: Introductionmentioning

confidence: 99%

Molecular Architectonics of Stereochemically Constrained π‐Complementary Functional Modules

et al. 2013

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The elucidation of the complex factors that govern recognition events at the molecular level represents a daunting challenge in our quest to master the art of pre‐programmed molecular assemblies. In this context, we present the molecular architectonics of thoughtfully designed amino acid appended functional molecules 1–5. Naphthalenediimide (NDI) and pyrene were employed as functional modules due to their unusual topological shape similarity as well as complementary π‐acidic and π‐basic character, respectively. In addition, we show that dyads of such unusual functional modules energetically favour alternate assembly in contrast to the predominant self‐sorted assembly observed for single‐component systems. Moreover, by incorporating minute structural mutations into the amino acid side‐chains of 1–5, we successfully tailored their assemblies into well‐defined supramolecular architectures, namely supercoiled helices, twisted nanoribbons, nanobelts, comb‐edged nanoflakes and nanosheets. A detailed analysis with the aid of experimental and theoretical studies has generated interesting insights into the factors that govern the recognition events at the molecular level.

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“…However, their stacking nature can lead to severely quenched emission111213141516, which has greatly hindered the exploitation of their properties and further applications. To fabricate emissive aggregates or solid-state materials, it has been common practice to weaken the π-π interactions of aromatic chromophores by the covalent attachment of substituents, e. g., bulky dendrons, into the aromatic rings, and it is quite efficient to fabricate highly fluorescent materials17181920212223, which, however, often involves difficult organic synthesis with multiple steps.…”

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confidence: 99%

A supramolecular approach to fabricate highly emissive smart materials

Yao

Kang

et al. 2013

Sci Rep

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The aromatic chromophores, for example, perylene diimides (PDIs) are well known for their desirable absorption and emission properties. However, their stacking nature hinders the exploitation of these properties and further applications. To fabricate emissive aggregates or solid-state materials, it has been common practice to decrease the degree of stacking of PDIs by incorporating substituents into the parent aromatic ring. However, such practice often involves difficultorganic synthesis with multiple steps. A supramolecular approach is established here to fabricate highly fluorescent and responsive soft materials, which has greatly decreases the number of required synthetic steps and also allows for a system with switchable photophysical properties. The highly fluorescent smart material exhibits great adaptivity and can be used as a supramolecular sensor for the rapid detection of spermine with high sensitivity and selectivity, which is crucial for the early diagnosis of malignant tumors.

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Amino Acid Derivatized Arylenediimides: A Versatile Modular Approach for Functional Molecular Materials

Cited by 96 publications

References 98 publications

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

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

Molecular Architectonics of Stereochemically Constrained π‐Complementary Functional Modules

A supramolecular approach to fabricate highly emissive smart materials

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