Polymorphism Controlled Singlet Fission in TIPS-Anthracene: Role of Stacking Orientation

Bhattacharyya, Kalishankar; Datta, Ayan

doi:10.1021/acs.jpcc.6b10075

Cited by 70 publications

(87 citation statements)

References 66 publications

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“…In addition, a new polymorph of TIPS ANT is identified (named TIPS ANTp in this work), revealing that different molecular packing can result from the same synthesis procedure (Landis et al, 2005). The occurrence of polymorphism in the case of TIPS anthracene compounds has also been observed recently by Bhattacharyya & Datta (2017). The position of the molecular substituents towards the external benzene rings is shown to influence the crystal morphology (i.e.…”

Section: Introductionsupporting

confidence: 59%

Synthesis, crystal structure, polymorphism and microscopic luminescence properties of anthracene derivative compounds

Moliterni

Altamura

Lassandro

et al. 2020

Acta Crystallogr B Struct Sci Cryst Eng Mater

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Anthracene derivative compounds are currently investigated because of their unique physical properties (e.g. bright luminescence and emission tunability), which make them ideal candidates for advanced optoelectronic devices. Intermolecular interactions are the basis of the tunability of the optical and electronic properties of these compounds, whose prediction and exploitation benefit from knowledge of the crystal structure and the packing architecture. Polymorphism can occur due to the weak intermolecular interactions, requiring detailed structural analysis to clarify the origin of observed material property modifications. Here, two silylethyne-substituted anthracene compounds are characterized by single-crystal synchrotron X-ray diffraction, identifying a new polymorph in the process. Additionally, laser confocal microscopy and fluorescence lifetime imaging microscopy confirm the results obtained by the X-ray diffraction characterization, i.e. shifting the substituents towards the external benzene rings of the anthracene unit favoursinteractions, impacting on both the morphology and the microscopic optical properties of the crystals. The compounds with more isolated anthracene units feature shorter lifetime and emission spectra, more similar to those of isolated molecules. The crystallographic study, supported by the optical investigation, sheds light on the influence of non-covalent interactions on the crystal packing and luminescence properties of anthracene derivatives, providing a further step towards their efficient use as building blocks in active components of light sources and photonic networks.

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Section: Introductionsupporting

confidence: 59%

Synthesis, crystal structure, polymorphism and microscopic luminescence properties of anthracene derivative compounds

Moliterni

Altamura

Lassandro

et al. 2020

Acta Crystallogr B Struct Sci Cryst Eng Mater

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“…So, pyracylene may support the idea of a singlet fission process, where a pair of correlated triplet excitons is formed from one singlet excitation on a molecule as E (S 1 ) is greater than 2* E (T 1 ). 24,25 However, as E ( T 2 ) is 0.1 eV lower than E (T 1 ), possibility of the triplet–triplet annihilation process cannot be ruled out for pyracylene. In Table 1, we compared the full CI results with the TDDFT results for pyracylene.…”

Section: Results and Discussionmentioning

confidence: 99%

Singlet and Triplet Excited State Energy Ordering in Cyclopenta-Fused Polycyclic Aromatic Hydrocarbons (CP-PAHs) Suitable for Energy Harvesting: An Exact Model and TDDFT Study

Naskar

Das

2017

ACS Omega

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We calculated the ground and low-lying excited states of cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs) using exact diagonalization in full configuration interaction (CI) within the model Pariser–Parr–Pople Hamiltonian as well as a time-dependent density functional theory technique. The CP-PAHs include acenapthylene, isomers of pyracylene, cycloocta-pentalene, and three isomers of dicyclo-pentacyclo-octenes (DCPCO). We used the inherent symmetries of these systems to calculate the energy ordering of the lowest singlet (S 1 ) and lowest triplet excited (T 1 ) states with respect to the ground state (S 0 ). The calculation shows that the lowest dipole allowed singlet absorption varies from 0.43 to 1.42 eV for most of these systems. Such an optical absorption range is very promising in harvesting solar radiation ranging from the visible to near-infrared region improving the efficiency of photovoltaic device application. The calculated optical gaps for pyracylene, acenapthylene, and two isomers of DCPCO are in very good agreement with experimental results reported in the literature. The calculated S 1 –T 1 energy gaps (Δ ST ) in cycloocta-pentalene and in the DCPCO isomers are very small ranging from 0.01 to 0.2 eV, which is highly desirable in improving their electroluminescence efficiency in light-emitting device applications.

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“…A likely rationale is based on the formation of an excimeric state as it resembles those known for excimers . Notably, its energy of 1.84 ± 0.05 eV would still be sufficient to support exergonic triplet formation via intermolecular SF …”

Section: Photophysical Characterization In Medium and High Concentratmentioning

confidence: 99%

“…A favorable configuration between two chromophores is crucial to achieve the appropriate coupling for intermolecular SF and between two chromophore units for intramolecular SF . In particular, π–π interactions facilitate the geometrical arrangement and/or stacking of the chromophores that, in turn, maximize the electronic coupling in the excited‐states …”

Section: Introductionmentioning

confidence: 99%

Intermolecular Singlet Fission in Unsymmetrical Derivatives of Pentacene in Solution

Casillas

Adam²,

Coto

et al. 2018

Advanced Energy Materials

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Intermolecular singlet fission (SF) is an electronically coupled process between two chromophores, where distance dependences are decisive in terms of rates and yields. In the current work, a family of pentacene derivatives featuring different functional groups have been designed, synthesized, and probed with respect to intermolecular SF in the low, medium, and high concentration regimes rather than in the solid state. By means of advanced photophysical techniques, global analysis modeling, and ab initio calculations, a model for intermolecular SF is postulated. The model is based on an early key intermediate, which involves the diffusional encounter between one pentacene in its singlet excited‐state with another one in its ground state and which features excimer characteristics. This is followed by a transformation into a coupled triplet excited‐state. The role of the functional group appended to pentacene is analyzed with respect to steric shielding of the pentacene core as a means to prevent photophysical degradation, as well as control diffusional encounter and, subsequently, SF. The findings demonstrate the potential of new molecular materials for SF, especially in solution studies, as well as the challenges of implementing them in energy conversion schemes due to the appearance of photodegradation processes that compete with SF.

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Polymorphism Controlled Singlet Fission in TIPS-Anthracene: Role of Stacking Orientation

Cited by 70 publications

References 66 publications

Synthesis, crystal structure, polymorphism and microscopic luminescence properties of anthracene derivative compounds

Synthesis, crystal structure, polymorphism and microscopic luminescence properties of anthracene derivative compounds

Singlet and Triplet Excited State Energy Ordering in Cyclopenta-Fused Polycyclic Aromatic Hydrocarbons (CP-PAHs) Suitable for Energy Harvesting: An Exact Model and TDDFT Study

Intermolecular Singlet Fission in Unsymmetrical Derivatives of Pentacene in Solution

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