Bond Ellipticity Alternation: An Accurate Descriptor of the Nonlinear Optical Properties of π-Conjugated Chromophores

Lopes, Thiago O.; Machado, Daniel F. S.; Risko, Chad; Brédas, Jean‐Luc; Oliveira, Heibbe C. B. de

doi:10.1021/acs.jpclett.8b00478

Cited by 25 publications

(9 citation statements)

References 26 publications

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“…These observations are thence rationalized to elucidate intraionic and interionic structure-property relationships in DAST and BP3 that control their second-order NLO function. A validation of these models was explored and this is presented in the Supplemental Material [14,[20][21][22][23][24][25][26][27][28][29][30]. We show that our findings validate the models, which in turn demonstrates the validity of constructing them for a vast range of prospective NLO materials.…”

Section: Scope Of Papersupporting

confidence: 62%

Multiphase structural models and hyperpolarizability calculations explain second-order nonlinear optical properties of stilbazolium ions

Ashcroft

Cole

Lin

et al. 2020

Phys. Rev. Materials

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Section: Scope Of Papersupporting

confidence: 62%

Multiphase structural models and hyperpolarizability calculations explain second-order nonlinear optical properties of stilbazolium ions

Ashcroft

Cole

Lin

et al. 2020

Phys. Rev. Materials

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“…On the other hand, for π-electrons delocalized across two planar aromatic structures, where some double-bond characters are expected in the bridging bond, it would be expected that preventing the loss of π-electron delocalization may lead to a steep barrier. To validate this assertion, the bond lengths (Figure ), bond ellipticities (BE; Figures and S11), and Mayer bond orders (MBO; Figure S10) of the bridge and adjoining bonds were evaluated.…”

Section: Resultsmentioning

confidence: 99%

Reconsidering the Roles of Noncovalent Intramolecular “Locks” in π-Conjugated Molecules

et al. 2021

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The extrinsic properties of organic semiconductors (OSC) are connected both to local and long-range thin-film morphologies. While it is desirable to synthetically regulate OSC solid-state structure, there remains limited understanding of the rich and complex relationships among the molecular structure of the chromophores that comprise the OSC and the functional parameters of the processing environment (e.g., solvent, solution composition, and temperature), each of which will impact the final OSC structure and characteristics. Here, we are interested in exploring how chromophore chemistry and the processing environment impact the structures of oligomers comprised of electron-rich donor and electron-deficient acceptor moieties, as conformational variations among these groups can impact OSC formation. Specifically, we make use of quantum-chemical calculations and molecular dynamics (MD) simulations to systematically investigate how variations in molecular design and processing chemistry influence the structure, dynamics, and aggregation tendencies of donor–acceptor (D–A) oligomers in solution. The investigation reveals preferential rotational isomer populations as a function of the oligomer chemistry, solvent environment, and oligomer concentration. Notably, questions are brought forward concerning the current emphasis on the roles of noncovalent intramolecular interactions in the design of OSC building blocks. Overall, the results provide an in-depth molecular-scale foundation to allow for thermodynamic and kinetic control of OSC morphology development through chromophore design and solvent optimization.

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“…In addition, distinct torsional force field parameters for the ground (S 0 ) and excited (S 1 ) states of Az11 were derived by employing Ph–NN–Ph torsional potentials calculated at the CASPT2 ab initio level, with the methodology reported in ref . Additionally, the FF bond equilibrium distances were modified to ensure close reproduction of the DFT bond lengths (with a mean absolute error of 0.006 Å for both trans and cis conformers; see the SI), a fundamental requirement for utilizing FF geometries in quantum chemical calculations of NLO properties, since those are strictly linked to the accurate description of bond lengths and bond length alternation. − …”

Section: Methodsmentioning

confidence: 99%

Nonlinear Optical Contrast in Azobenzene-Based Self-Assembled Monolayers

et al. 2019

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Conjugated organic photochromes such as azobenzene derivatives can show remarkable nonlinear optical (NLO) properties and rapid responses, two essential requirements for the realization of optoelectronic switching devices. These applications also require the control of the molecular organization over the micrometric scale, which in principle can be achieved by arranging chromophore units in self-assembled monolayers (SAMs). To rationalize the interplay between the NLO responses of isolated molecules and those of photoresponsive materials, we implement here a computational approach combining molecular dynamics simulations and DFT calculations for predicting the NLO responses of azobenzene-based SAMs with different surface densities. We show that collective switching of the chromophores is indeed possible, even though trans → cis photoisomerization yields decrease when increasing the chromophore concentration. The magnitude of the second-order NLO response of trans SAMs is dominated by the component normal to the surface, which is considerably larger than the parallel one and significantly increases with the packing density. Photoswitching has the neat effect of halving the first hyperpolarizability, allowing for large NLO contrasts exploitable for storing and reading information in selected portions of the surface.

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Bond Ellipticity Alternation: An Accurate Descriptor of the Nonlinear Optical Properties of π-Conjugated Chromophores

Cited by 25 publications

References 26 publications

Multiphase structural models and hyperpolarizability calculations explain second-order nonlinear optical properties of stilbazolium ions

Multiphase structural models and hyperpolarizability calculations explain second-order nonlinear optical properties of stilbazolium ions

Reconsidering the Roles of Noncovalent Intramolecular “Locks” in π-Conjugated Molecules

Nonlinear Optical Contrast in Azobenzene-Based Self-Assembled Monolayers

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