Compact TCBD based molecules and supramolecular assemblies for third-order nonlinear optics

Beels, Marten; Fleischman, Michelle S.; Biaggio, Ivan; Breiten, Benjamin; Jordan, Markus; Diederich, François

doi:10.1364/ome.2.000294

Cited by 35 publications

(34 citation statements)

References 23 publications

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“…IV) representing the fundamental limit [9]. The specific third-order polarizability y is obtained by dividing the same experimental yrot by the mass of the molecule [10,11], and it describes the potential of obtaining large bulk third-order susceptibilities if the molecules can be combined into a dense supramolecular assembly [11][12][13][14]. Similar definitions for assessing two-photon absorption will be discussed in Sec.…”

Section: T (3)mentioning

confidence: 99%

“…1. They are all characterized by efficient off-resonant third-order nonlinearities [10][11][12][13]15] that have been shown to be very high compared to both the off-resonant fundamental limit and the size of the molecule.…”

Section: Moleculesmentioning

confidence: 99%

“…1 [10,12,13,15,16], and their dem onstrated significance for applications [12,[17][18][19], m otivate a more com plete characterization o f the behavior o f their nonlinear response w hen the optical w avelengths start approaching the first tw o-photon absorption resonance. [6][7][8]20,21], For third-order effects, the off-resonant funda [20] to the case o f the m olecules and experim ents discussed in this work.…”

Section: Moleculesmentioning

confidence: 99%

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Two-photon absorption and spectroscopy of the lowest two-photon transition in small donor-acceptor–substituted organic molecules

et al. 2015

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We determine the dispersion of the third-order polarizability of small donor-acceptor substituted organic molecules using wavelength-dependent degenerate four-wave mixing experiments in solutions with varying concentrations. We find that donor-acceptor-substituted molecules that are characterized by extremely efficient off-resonant nonlinearities also have a correspondingly high two-photon absorption cross section. The width and shape of the first two-photon resonance for these noncentrosymmetric molecules follows what is expected from their longest wavelength absorption peak, and the observed two-photon absorption cross sections are record high when compared to the available literature data, the size of the molecule, and the fundamental limit for two-photon absorption to the lowest excited state, which is essentially determined by the number of conjugated electrons and the excited-state energies. The two-photon absorption of the smallest molecule, which only has 16 electrons in its conjugated system, is one order of magnitude larger than for the molecule called AF-50, a reference molecule for two-photon absorption [O.-K. Kim et al., Chem. Mater. 12, 284 (2000)].

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Section: T (3)mentioning

confidence: 99%

Section: Moleculesmentioning

confidence: 99%

Section: Moleculesmentioning

confidence: 99%

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Two-photon absorption and spectroscopy of the lowest two-photon transition in small donor-acceptor–substituted organic molecules

et al. 2015

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“…Phase disruption is proposed as a new general principle for the design of molecules, nanowires and any quasi-1D quantum system with large intrinsic response and does not require charge donor-acceptors at the ends. © The design and realization of ultrafast nonlinear optical materials with large responses to optical frequency electric fields remains an active field of pure and applied research [1][2][3][4]. To date, no general design rules for obtaining large nonlinearities from any structure have been articulated, and the response of materials remains well below that allowed by quantum physics.…”

mentioning

confidence: 99%

“…Normalized to its maximum value, the sum over states expression for the intrinsic first hyperpolarizability along the x-axis may be written as [5] β xxx = 3 3 where the sum is over all states, x nℓ is the n, ℓ element of the position matrix withx = x − x 00 , E n0 = E n − E 0 is the difference in energy of eigenstates n and 0, N is the number of electrons and m their mass. We include as many as 100 energy eigenstates to calculate β, but systems with large β are always well approximated using only three states.…”

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confidence: 99%

Phase disruption as a new design paradigm for optimizing the nonlinear-optical response

2015

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The intrinsic optical nonlinearities of linear structures, including conjugated chain polymers and nanowires, are shown to be dramatically enhanced by the judicious placement of a charge diverting path sufficiently short to create a large phase disruption in the dominant eigenfunctions along the main path of probability current. Phase disruption is proposed as a new general principle for the design of molecules, nanowires and any quasi-1D quantum system with large intrinsic response and does not require charge donor-acceptors at the ends. © The design and realization of ultrafast nonlinear optical materials with large responses to optical frequency electric fields remains an active field of pure and applied research [1][2][3][4]. To date, no general design rules for obtaining large nonlinearities from any structure have been articulated, and the response of materials remains well below that allowed by quantum physics. In this letter, we propose a general principle that may explain why modern molecules fall short of their potential and use it to demonstrate simple structures with nonlinear responses approaching the physical limits.The off-resonance electronic nonlinear optical response of a molecule is completely determined by its energy spectrum and transition moments. Normalized to its maximum value, the sum over states expression for the intrinsic first hyperpolarizability along the x-axis may be written as [5] where the sum is over all states, x nℓ is the n, ℓ element of the position matrix withx = x − x 00 , E n0 = E n − E 0 is the difference in energy of eigenstates n and 0, N is the number of electrons and m their mass. We include as many as 100 energy eigenstates to calculate β, but systems with large β are always well approximated using only three states. For brevity, we focus on the first hyperpolarizability, though our results also hold for the second hyperpolarizability, γ xxxx . For the remainder of this letter, all hyperpolarizabilities are divided by their maximum values and represent intrinsic tensor properties. It is evident from Eqn.(1) that a system optimized for nonlinear optics will necessarily have eigenfunctions with a large degree of overlap as well as a large change of dipole moment between contributing levels. This is an essential trade-off to achieve a large response. It is generally recognized that the hyperpolarizabilities of most molecules fall at least 30 times short of the limits. [5,6]. Monte Carlo simulations discovered the optimum energy spectrum for such molecules and provided a strong indicator of the origin of the gap [7]. Optimization of the effective potential energy an electron experiences across the main direction of a quasi-linear molecule showed that the hyperpolarizabilities may be increased by tuning a few parameters [8], by modulation of conjugation along a chain [9], or by donor-acceptor substitution and insertion of spacers [10]. However, there is no general rule about how to construct the ideal potential energy profile across a molecule to maximize the nonlinea...

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Die [2+2]‐Cycloadditions‐Retroelektrocyclisierungs(CA‐RE)‐Klick‐Reaktion: ein einfacher Zugang zu molekularen und polymeren Push‐pull‐Chromophoren

Michinobu

Diederich

2018

Angewandte Chemie

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Die [2+2]‐Cycloadditions‐Retroelektrocyclisierungs(CA‐RE)‐Reaktion von elektronenreichen Alkinen mit elektronenarmen Alkenen ist ein effizientes Verfahren zur Bildung nichtplanarer Donor‐Akzeptor‐Chromophore sowohl in molekularen als auch in polymeren Plattformen. Diese Chromophore zeigen ansprechende Eigenschaften, wie intramolekulare Charge‐Transfer(ICT)‐Banden, nichtlineare optische Eigenschaften und Redox‐Eigenschaften zur Verwendung in elektronischen und optoelektronischen Funktionseinheiten der nächsten Generation. Dieser Aufsatz fasst die Entwicklung der CA‐RE‐Reaktion zusammen, beginnend mit den anfänglichen Berichten über Organometallverbindungen bis hin zu rein organischen Systemen. Die strukturellen Voraussetzungen für schnelle Umsetzungen in hohen Ausbeuten, Merkmale echter Klick‐Chemie, werden anhand von Beispielen dargelegt, die die breiten möglichen Alkin‐ und Alkensubstitutionsmuster belegen. Die CA‐RE‐Klick‐Reaktion wurde erfolgreich in der Polymerchemie eingesetzt. Die gebildeten polymeren Push‐pull‐Chromophore finden dabei zahlreiche interessante Anwendungen.

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Compact TCBD based molecules and supramolecular assemblies for third-order nonlinear optics

Cited by 35 publications

References 23 publications

Two-photon absorption and spectroscopy of the lowest two-photon transition in small donor-acceptor–substituted organic molecules

Two-photon absorption and spectroscopy of the lowest two-photon transition in small donor-acceptor–substituted organic molecules

Phase disruption as a new design paradigm for optimizing the nonlinear-optical response

Die [2+2]‐Cycloadditions‐Retroelektrocyclisierungs(CA‐RE)‐Klick‐Reaktion: ein einfacher Zugang zu molekularen und polymeren Push‐pull‐Chromophoren

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