Physical Vapor Deposited Films of a Perylene Derivative: Supramolecular Arrangement and Thermal Stability

Fernandes, José Diego; Aléssio, Priscila; Silva, Matheus Rodrigues Medeiros; Aroca, Ricardo F.; Souza, Agda Eunice de; Constantino, Carlos J. L.

doi:10.1590/1980-5373-mr-2016-0692

Cited by 10 publications

(6 citation statements)

References 46 publications

(66 reference statements)

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“…The relatively good agreement between experimental and simulated Raman spectra of the rigid tetramer indicate that either or both of the PDI–spiro–PDI wings are planarized, although the extent is not certain because of the idealized model tetramers used in these calculations. Cursory comparison to Raman spectra of single PDI systems reveals similarities with the rigid Raman pattern, , but this is complicated by resonance enhancement effects in the former. Nonetheless, we expect that actual rigid tetramer geometries may experience minor alterations due to the presence of branched alkyl groups on the imide positions of each PDI unit.…”

Section: Results and Discussionmentioning

confidence: 96%

Conformational Flexibility Determines Electronic Coupling and Charge Transfer Character in Single Propeller-Shaped Perylene Diimide Tetramer Arrays

Walwark

Datko

et al. 2018

J. Phys. Chem. C

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We investigate the effect of molecular geometry and conformational flexibility on electronic coupling and charge transfer interactions within propeller-shaped perylene diimide (PDI) tetramer arrays differing by the number of covalent linkages to a central spirobifluorene core. Electronic spectra of tetramers with one (“floppy”) or two (“rigid”) bay covalent linkages display evidence of charge transfer character in either ground or excited states. Floppy tetramers exhibit marked red-shifted and broadened absorption features that we assign as overlapping inter-PDI charge transfer and PDI-centered π–π* transitions, whereas rigid tetramers retain features similar to single PDI molecules, albeit with broader line widths. Interestingly, both tetramers exhibit charge transfer character in their fluorescence emission, but this is most prominent in the rigid tetramer, which displays dominant long-lived excimer behavior in addition to a minority component resembling single PDI-like emission. We then use single-molecule spectroscopy and imaging to understand how conformational-dependent charge transfer properties influence tetramer photophysics. Over 90% of single rigid tetramers display telegraphic (i.e., two-level) blinking behavior with relatively short “on” times compared to ∼60% of single floppy tetramer transients, which tend to exhibit emission from multiple levels. Electronic structure simulations were next performed to aid in the assignment of electronic transitions and photophysical behavior. Floppy tetramer canonical and natural transition orbitals reveal remarkable similarities with significant charge transfer character in the lowest energy excited states involving transverse PDI units and appreciable spirobifluorene contributions in the ground electronic state. Rigid tetramers exhibit greater electronic delocalization, and calculated absorption transition energies show good agreement with experiment, although excited-state interactions are less straightforward to discern from simulations. Raman spectroscopy and polarization-dependent single-molecule spectroscopy were also performed, supporting assignments based on theoretical predictions and electronic spectroscopy results. Overall, we demonstrate the importance of molecular geometry and conformational flexibility of multichromophore arrays in determining the nature of electronic interactions in ground and excited states, which can eventually be harnessed to improve performance attributes at the materials level.

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Section: Results and Discussionmentioning

confidence: 96%

Conformational Flexibility Determines Electronic Coupling and Charge Transfer Character in Single Propeller-Shaped Perylene Diimide Tetramer Arrays

Walwark

Datko

et al. 2018

J. Phys. Chem. C

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“…Therefore, it was verified that the roughness of the PhPTCD LS film is greater than that of the BuPTCD, suggesting that the molecular structure may have been responsible for the differences observed between the morphologies. In addition, it is important to emphasize that the roughness values of both films obtained in this work are significantly higher than those found for PVD films of the same perylene derivatives. ,, …”

Section: Resultsmentioning

confidence: 55%

“…When these results are compared with those found for the BuPTCD and PhPTCD molecules in the form of films deposited via PVD, it is observed that the LS and PVD films of BuPTCD have the same head-on molecular organization . However, while the LS film has a head-on molecular organization, the PhPTCD PVD film has a face-on molecular organization …”

Section: Resultsmentioning

confidence: 73%

“…In addition, it is important to emphasize that the roughness values of both films obtained in this work are significantly higher than those found for PVD films of the same perylene derivatives. 12,42,43 Molecular Organization. The infrared absorption spectra of the BuPTCD and PhPTCD LS films were obtained and combined with the surface selection rules in order to investigate the molecular organization of the films.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…48 However, while the LS film has a head-on molecular organization, the PhPTCD PVD film has a face-on molecular organization. 43 Crystallinity. The DRX technique was used in the LS films of BuPTCD and PhPTCD deposited on quartz substrate at 30 and 40 nm (thickness), respectively, with the intent of investigating whether the films present any degree of crystallinity (Figure 10).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

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Langmuir–Schaefer Perylene Derivative Films: Influence of the Molecular Chemical Structure on the Supramolecular Arrangement

et al. 2021

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Since the optical and electrical properties of organic thin films devices depend on their supramolecular arrangement and the molecular chemical structure, the understanding of such characteristics is essential for the optimization of these devices. In this study, we determine the supramolecular arrangement of thin films produced using the Langmuir–Schaefer (LS) technique and explain how its supramolecular arrangement is affected by the molecular chemical structure using two perylene derivatives: bis-butylimide (BuPTCD) and bis-phenethylimide (PhPTCD). The optical absorption measurements reveal that both films grow homogeneously and indicate that the presence of H aggregates (forbidden emission) is higher for BuPTCD LS film than for PhPTCD LS film. Atomic force microscopic analysis shows that the PhPTCD LS film is rougher than the BuPTCD film. In addition, FTIR analyses indicate that both films have head-on molecular organization. XRD patterns reveal that both the BuPTCD LS film and the PhPTCD LS film are crystalline, but that crystallinity is more prevalent in the BuPTCD LS film. Thus, the results show that the difference presented in the chemical structures leads the films to have different supramolecular arrangements, with consequences for their optical properties.

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Polydiacetylene–Perylenediimide Supercapacitors

et al. 2020

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Organic supercapacitors have attracted interest as promising “green” and efficient components in energy storage applications. A polydiacetylene derivative coupled with reduced graphene oxide was employed, for the first time, to generate an organic pseudocapacitance‐based supercapacitor that exhibited excellent electrochemical properties. Specifically, diacetylene monomers were functionalized with perylenediimide (PDI), spontaneously forming elongated microfibers. Following polymerization through UV irradiation, the PDI–polydiacetylene microfibers were interspersed with reduced graphene oxide (rGO), generating a porous electrode material exhibiting a high surface area and facilitating efficient ion diffusion, both essential preconditions for supercapacitor applications. We show that PDI–polydiacetylene has an important role in enhancing the electrochemical properties as a supercapacitor electrode. Besides stabilizing the microporous electrode organization, the delocalized π electrons in both the PDI residues and conjugated network of the polydiacetylene contributed to a significantly higher capacitance (specific capacitance >600 F g−1 at 1 A g−1 current density), longer discharge time, and high power density. The PDI–polydiacetylene‐rGO electrodes were employed in a functional supercapacitor device.

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Physical Vapor Deposited Films of a Perylene Derivative: Supramolecular Arrangement and Thermal Stability

Cited by 10 publications

References 46 publications

Conformational Flexibility Determines Electronic Coupling and Charge Transfer Character in Single Propeller-Shaped Perylene Diimide Tetramer Arrays

Conformational Flexibility Determines Electronic Coupling and Charge Transfer Character in Single Propeller-Shaped Perylene Diimide Tetramer Arrays

Langmuir–Schaefer Perylene Derivative Films: Influence of the Molecular Chemical Structure on the Supramolecular Arrangement

Polydiacetylene–Perylenediimide Supercapacitors

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