Photogeneration of Octacene and Nonacene

Tönshoff, Christina; Bettinger, Holger F.

doi:10.1002/anie.200906355

Cited by 332 publications

(218 citation statements)

References 39 publications

Supporting

Mentioning

205

Contrasting

Order By: Relevance

“…For higher acenes, we predict the excitation energy to be 1.58, 1.36, 1.20, 1.08, 0.96-0.99, and 0.93-0.94 eV for 7, 8, 9, 10, 11, and 12, respectively. We notice that some experimental data have been available for 7, 8, and 9 in polymer matrix or inert gas matrix (40,41,101), and there has been a fairly accurate DFT/MRCI study (63). It seems that our predictions might be slightly too low ( ≈ 0.2 eV) for these higher acenes.…”

Section: St Energy Gapmentioning

confidence: 79%

“…Even though the synthesis of hexacene (6) was reported more than 70 y ago (37,38), a scheme that is easy to reproduce was not achieved until 2007 through a photochemical process in a polymer matrix, which helps retain the highly reactive product 6 (39). Similar schemes were also successfully applied to the synthesis of three even less stable species-heptacene (7) (40), octacene (8), and nonacene (9) (41). Although the synthesis of decacene (10) and undecacene (11) with 10 or more fused-benzene rings will be more challenging and has not yet been achieved, the exploration of higher acenes and their derivatives continues unabated.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Nature of ground and electronic excited states of higher acenes

Yang

Davidson

Yang

2016

Proc. Natl. Acad. Sci. U.S.A.

169

208

View full text Add to dashboard Cite

Higher acenes have drawn much attention as promising organic semiconductors with versatile electronic properties. However, the nature of their ground state and electronic excited states is still not fully clear. Their unusual chemical reactivity and instability are the main obstacles for experimental studies, and the potentially prominent diradical character, which might require a multireference description in such large systems, hinders theoretical investigations. Here, we provide a detailed answer with the particleparticle random-phase approximation calculation. The 1 A g ground states of acenes up to decacene are on the closed-shell side of the diradical continuum, whereas the ground state of undecacene and dodecacene tilts more to the open-shell side with a growing polyradical character. The ground state of all acenes has covalent nature with respect to both short and long axes. The lowest triplet state 3 B 2u is always above the singlet ground state even though the energy gap could be vanishingly small in the polyacene limit. The bright singlet excited state 1 B 2u is a zwitterionic state to the short axis. The excited 1 A g state gradually switches from a doubleexcitation state to another zwitterionic state to the short axis, but always keeps its covalent nature to the long axis. An energy crossing between the 1 B 2u and excited 1 A g states happens between hexacene and heptacene. Further energetic consideration suggests that higher acenes are likely to undergo singlet fission with a low photovoltaic efficiency; however, the efficiency might be improved if a singlet fission into multiple triplets could be achieved.higher acenes | diradical | double excitation | particle-particle random-phase approximation | charge-transfer excitation

show abstract

Section: St Energy Gapmentioning

confidence: 79%

mentioning

confidence: 99%

Nature of ground and electronic excited states of higher acenes

Yang

Davidson

Yang

2016

Proc. Natl. Acad. Sci. U.S.A.

169

208

View full text Add to dashboard Cite

show abstract

“…Although Clar reported [14] the synthesis of hexacene in 1942, its existence remained controversial until 2006, when its synthesis was finally reproduced in stabilizing matrices [13,15]. In 2009, the polyacene series from pentacene through heptacene was produced and investigated in a matrixisolation study by Mondal et al [13] In 2010 Tönshoff and Bettinger [16] reported the production, ultraviolet (UV) and infrared (IR) spectroscopic characterization of octacene and nonacene in an argon matrix.…”

Section: Introductionmentioning

confidence: 99%

Infrared vibrational and electronic transitions in the dibenzopolyacene family

Mattioda

Bauschlicher

Bregman

et al. 2014

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

View full text Add to dashboard Cite

“…Due to the recent progress in synthesis methodology, oligoacenes up to length N R = 9 (nonacene) have already been produced. 10,11 Previously, we have found that linear (oligo)acenes exhibit oscillations in the N R (or length) dependence of optical excitation gaps. 12 Oscillations of electronic properties with the geometric size of a nano-system are per se frequently encountered.…”

Section: Introductionmentioning

confidence: 99%

Incommensurate quantum-size oscillations in acene-based molecular wires—Effects of quantum fluctuations

Schmitteckert

Thomale

Korytár

et al. 2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

Destructive quantum interference in electron transport: A reconciliation of the molecular orbital and the atomic orbital perspective The Journal of Chemical Physics 146, 092308 (2017) Molecular wires of the acene-family can be viewed as a physical realization of a two-rung ladder Hamiltonian. For acene-ladders, closed-shell ab initio calculations and elementary zone-folding arguments predict incommensurate gap oscillations as a function of the number of repetitive ring units, N R , exhibiting a period of about ten rings. Results employing open-shell calculations and a mean-field treatment of interactions suggest anti-ferromagnetic correlations that could potentially open a large gap and wash out the gap oscillations. Within the framework of a Hubbard model with repulsive on-site interaction, U, we employ a Hartree-Fock analysis and the density matrix renormalization group to investigate the interplay of gap oscillations and interactions. We confirm the persistence of incommensurate oscillations in acene-type ladder systems for a significant fraction of parameter space spanned by U and N R .

show abstract

Photogeneration of Octacene and Nonacene

Cited by 332 publications

References 39 publications

Nature of ground and electronic excited states of higher acenes

Nature of ground and electronic excited states of higher acenes

Infrared vibrational and electronic transitions in the dibenzopolyacene family

Incommensurate quantum-size oscillations in acene-based molecular wires—Effects of quantum fluctuations

Contact Info

Product

Resources

About