Rational design of doubly-bridged chromophores for singlet fission and triplet–triplet annihilation

Ito, Shinichiro; Nagami, Takanori; Nakano, Masayoshi

doi:10.1039/c7ra06032g

Cited by 16 publications

(16 citation statements)

References 98 publications

(192 reference statements)

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“…Ito et al. continued applying the same method to investigate quantum interference in structures with two chromophore units connected by two linkers . The two linkers analog of Equation (16) reads:

true t_{i j}^{mediated} \approx c_{μ^{'} (1) i} c_{ν^{'} (1) j} β^{2} ((), \frac{c_{μ (1) H_{L}} c_{ν (1) H_{L}}}{E - E_{H_{L (1)}}} - \frac{c_{μ L_{normalL (1)}} c_{ν L_{normalL (1)}}}{E_{L_{L (1)}} - E}) + c_{μ^{'} (2) i} c_{ν^{'} (2) j} β^{2} ((), \frac{c_{μ (2) H_{L}} c_{ν (2) H_{L}}}{E - E_{H_{L (2)}}} - \frac{c_{μ L_{normalL (2)}} c_{ν L_{normalL (2)}}}{E_{L_{L (2)}} - E})

…”

Section: Exploration For Singlet Fission Mechanisms Through Electronisupporting

confidence: 93%

See 1 more Smart Citation

Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

2018

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In this Review article, a survey is given for theoretical studies in the subject of singlet fission. Singlet fission converts one singlet exciton to two triplet excitons. With the doubled number of excitons and the longer lifetime of the triplets, singlet fission provides an avenue to improve the photoelectric conversion efficiency in organic photovoltaic devices. It has been a subject of intense research in the past decade. Theoretical studies play an essential role in understanding singlet fission. This article presents a Review of theoretical studies in singlet fission since 2006, the year when the research interest in this subject was reignited. Both electronic structure and dynamics studies are covered. Electronic structure studies provide guidelines for designing singlet fission chromophores and insights into the couplings between single‐ and multi‐excitonic states. The latter provides fundamental knowledge for engineering interchromophore conformations to enhance the fission efficiency. Dynamics studies reveal the importance of vibronic couplings in singlet fission.

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true t_{i j}^{mediated} \approx c_{μ^{'} (1) i} c_{ν^{'} (1) j} β^{2} ((), \frac{c_{μ (1) H_{L}} c_{ν (1) H_{L}}}{E - E_{H_{L (1)}}} - \frac{c_{μ L_{normalL (1)}} c_{ν L_{normalL (1)}}}{E_{L_{L (1)}} - E}) + c_{μ^{'} (2) i} c_{ν^{'} (2) j} β^{2} ((), \frac{c_{μ (2) H_{L}} c_{ν (2) H_{L}}}{E - E_{H_{L (2)}}} - \frac{c_{μ L_{normalL (2)}} c_{ν L_{normalL (2)}}}{E_{L_{L (2)}} - E})

…”

Section: Exploration For Singlet Fission Mechanisms Through Electronisupporting

confidence: 93%

“… Schematic representations of the four cases of interlinker interference discussed in Ref. . The phases of the chromophore unit's HOMO and LUMO at the connecting sites are indicated by white (positive) and black (negative) circles.…”

Section: Exploration For Singlet Fission Mechanisms Through Electronimentioning

confidence: 99%

Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

2018

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“…1,[12][13][14][15] Subsequent evolution controlled by the magnetic dipole-dipole interaction leads to the formation of separate, triplet excitons in a process where several states of different spin multiplicity interact in a complex interplay. 1,[16][17][18][19][20][21][22][23][24][25] The complexity of the process has motivated an important theoretical research effort to decipher SF, which implies identifying the electronic states participating in the process, their roles [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] and coupling mechanisms 1,[42][43][44][45][46][47][48][49][50][51] and characterizing the dynamics, including the role of mode specific aspects of the nuclear motion, conical intersections, interference and decoherence effects. ...…”

Section: Introductionmentioning

confidence: 99%

“…1,[16][17][18][19][20][21][22][23][24][25] The complexity of the process has motivated an important theoretical research effort to decipher SF, which implies identifying the electronic states participating in the process, their roles [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] and coupling mechanisms 1,[42][43][44][45][46][47][48][49][50][51] and characterizing the dynamics, including the role of mode specific aspects of the nuclear motion, conical intersections, interference and decoherence effects. 14,15,28,40,41,43,47, As a result of this collective research effort, key electronic and str...…”

Section: Introductionmentioning

confidence: 99%

Quantum dynamical simulation of intramolecular singlet fission in covalently coupled pentacene dimers

Reddy

Coto

Thoss

2019

The Journal of Chemical Physics

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Spain b)We analyze the dynamics of intramolecular singlet fission in a series of pentacenebased dimers consisting of two pentacene-like chromophores covalently bonded to a phenylene linker in ortho, meta and para positions. The study uses a quantum dynamical approach that employs a model vibronic Hamiltonian whose parameters are obtained using multireference perturbation theory methods. The results highlight the different role of the direct and mediated mechanism in these systems, showing that the population rate of the multiexcitonic state, corresponding to the first step of the intramolecular singlet fission process, occurs mainly through a superexchange-like mechanism involving doubly excited or charge transfer states that participate in the process in a virtual way. In addition, the systems investigated provide insight into roles that built-in geometrical constraints and the electronic structure of the spacer play in the intramolecular singlet fission process.

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“…[1] Aside from these energy relations, other electronic and structural parameters such as the diradical character of the dye, overlap of the electron density clouds, type of crystal packing in organic crystals or nature of the linker (conjugated, cross-conjugated or non-conjugated) and interference effects in covalently bonded dimeric dyes have also been identified as relevant factors for the design of SF-active dyes. [1,7,8,[16][17][18][19][20] In this respect, different families of compounds have been shown to fulfill these conditions and, therefore, have been considered as potential candidates to exhibit efficient SF. [1,2] From all these families, acenes have been one of the most investigated compounds exhibiting SF and among them, pentacene derivatives have been thoroughly analyzed.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of intramolecular singlet fission in xanthene-bonded pentacene dimers

2018

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Singlet fission is a spin-allowed process by which two non-interacting triplet excitons are generated from a singlet exciton. This type of multiexciton generation mechanism may have the potential to overcome the Shockley-Queisser limit and could enable the development of more efficient solar cells. In this contribution, we analyze intramolecular singlet fission in two modified pentacene dimers covalently bonded to a xanthene spacer employing density functional theory and multireference perturbation theory methods. The systems investigated differ in the electronic structure and bulkiness of the substituents used and in this work we analyze the impact that these aspects have in the relative contributions of the direct and mediated mechanisms to the intramolecular singlet fission.

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Rational design of doubly-bridged chromophores for singlet fission and triplet–triplet annihilation

Abstract: A novel multiple-bridging realizes rational molecular design for efficient singlet fission and triplet–triplet annihilation.

Cited by 16 publications

References 98 publications

Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

Quantum dynamical simulation of intramolecular singlet fission in covalently coupled pentacene dimers

Theoretical study of intramolecular singlet fission in xanthene-bonded pentacene dimers

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