Enhanced Two‐Photon Absorption of Organic Chromophores: Theoretical and Experimental Assessments

Terenziani, Francesca; Katan, Claudine; Badaeva, Ekaterina; Tretiak, Sergei; Blanchard‐Desce, Mireille

doi:10.1002/adma.200800402

Cited by 535 publications

(586 citation statements)

References 321 publications

(518 reference statements)

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“…Indeed, it has been shown that increasing the "push-pull" character of the π-conjugated skeleton usually leads to an increase in σ TPA in dipolar molecules. [7][8][9][10][11] Therefore, the idea of replacing the fluorenyl unit by a more donating fragment arises naturally.…”

Section: Introductionmentioning

confidence: 99%

“…Among them, ruthenium-nitrosyl complexes have been recognized as the most promising candidates in relation to their generally low toxicity, good stability, and ability to release exclusively NO· under light irradiation, [6] taking advantage of the noninvasive and highly controllable characteristics of light. Additionally, although most NO· donors require to be irradiated in the 300-500 nm domain, the use of the two-photon absorption (TPA) technique, [7][8][9][10][11] in which the molecules simultaneously absorb two photons instead of one, allows the use of optical radiation at the double of wavelength, that is, the 600-1200 nm therapeutic window tiary amine in the carbazole unit leads to redshifted chargetransfer transitions towards the electron-withdrawing Ru-NO fragment and hence enhanced two-photon absorption (TPA) properties. In contrast, the quantum yield of the NO· photorelease process is lower for the carbazole-containing complex.…”

Section: Introductionmentioning

confidence: 99%

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Comparison of Carbazole and Fluorene Donating Effects on the Two‐Photon Absorption and Nitric Oxide Photorelease Capabilities of a Ruthenium–Nitrosyl Complex

et al. 2017

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A ruthenium-nitrosyl derivative of formula [Ru II (CzT)(bipy)(NO)](PF 6 ) 3 [CzT = 4′-(N-ethylcarbazol-3-yl)-2,2′:6′,2′′-terpyridine, bipy = 2,2′-bipyridine] has been synthesized and fully characterized, and compared with the previously reported [Ru II (FT)(bipy)(NO)](PF 6 ) 3 complex [FT = 4′-(9,9-dihexyl-9H-fluoren-2-yl)-2,2′:6′,2′′-terpyridine]. Additionally, the Xray crystal structure of [Ru II (CzT)(bipy)(NO 2 )](PF 6 ), the precursor of [Ru II (CzT)(bipy)(NO)](PF 6 ) 3 , is reported. The presence of a ter-

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Comparison of Carbazole and Fluorene Donating Effects on the Two‐Photon Absorption and Nitric Oxide Photorelease Capabilities of a Ruthenium–Nitrosyl Complex

et al. 2017

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“…[3][4][5] The development of these applications relies on the quest for molecules with high TPA cross sections at a desirable wavelength. 5,6 Chakrabarti and Ruud found that intermolecular chargetransfer (ICT) transitions can lead to high TPA cross sections in supermolecular π-stacking systems. 7,8 Indeed, they found that the cooperative effect of two aromatic molecules can tune the absorption wavelength and enhance the TPA cross sections relative to the single substituents in fullerene-buckycatcher 7 and molecular tweezer 8 complexes.…”

Section: Introductionmentioning

confidence: 99%

Intermolecular charge transfer enhances two-photon absorption in yellow fluorescent protein

Beerepoot

Friese

Ruud

2014

Phys. Chem. Chem. Phys.

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We present a quantum chemical study of the two-photon absorption (TPA) properties of yellow fluorescent protein (YFP), a mutant of the extensively studied green fluorescent protein. The aromatic chromophore of YFP has a π-stacking interaction with the aromatic ring of a tyrosine residue (Tyr203) in a parellel-displaced structure with a distance of about 3.4Å. We study the TPA spectrum of the π-stacking system of YFP using the well-established Coulomb-attenuated B3LYP density functional (CAM-B3LYP) and the second-order approximate coupled-cluster model CC2. This work presents both the first comprehensive study of the two-photon absorption spectrum of YFP and the largest-scale coupled-cluster calculation of two-photon absorption that has ever been performed. We analyze the intermolecular charge-transfer (ICT) transitions in this stacked system and show that the ICT transitions are an important mechanism for enhancing the TPA cross sections in YFP. We investigate the distance dependence of the ICT transitions and show that their TPA cross sections are strongly dependent on the separation of the aromatic moieties. This provides a means for tuning the TPA properties of YFP and other structurally related fluorescent proteins through molecular engineering.

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“…The observed difference in anisotropy results from the torsional disorder and symmetry of the structures of these branched chromophores, which lead to the nondegenerate energy levels. 27,44,71 The energy transfer then occurs among these nondegenerated ICT states, which results in a large decrease of anisotropy value during energy transfer.…”

mentioning

confidence: 99%

“…Both symmetry-breaking phenomena in excited state (caused by vibrational relaxation and solvation) and disorder-induced symmetry lowering (caused by ground state solute−solvent interaction) have been reported to contribute to the excitation localization. [25][26][27][42][43][44]64,65 In order to track down the excited state energy redistribution and the interbranch interaction of the multibranched molecules, it is instructive to determine the direction of molecular transition dipole moment and polarization of the spectrum.…”

mentioning

confidence: 99%

Localized Emitting State and Energy Transfer Properties of Quadrupolar Chromophores and (Multi)Branched Derivatives

Yan

Chen

et al. 2012

J. Phys. Chem. A

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In order to better understand the nature of intramolecular charge and energy transfer in multibranched molecules, we have synthesized and studied the photophysical properties of a monomer quadrupolar chromophore with donor−acceptor−donor (D−A−D) electronic push−pull structure, together with its V-shaped dimer and star-shaped trimers. The comparison of steady-state absorption spectra and fluorescence excitation anisotropy spectra of these chromophores show evidence of weak interaction (such as charge and energy transfer) among the branches. Moreover, similar fluorescence and solvation behavior of monomer and branched chromophores (dimer and trimer) implies that the interaction among the branches is not strong enough to make a significant distinction between these molecules, due to the weak interaction and intrinsic structural disorder in branched molecules. Furthermore, the interaction between the branches can be enhanced by inserting π bridge spacers (−CC− or −CC−) between the core donor and the acceptor. This improvement leads to a remarkable enhancement of two-photon cross-sections, indicating that the interbranch interaction results in the amplification of transition dipole moments between ground states and excited states. The interpretations of the observed photophysical properties are further supported by theoretical investigation, which reveal that the changes of the transition dipole moments of the branched quadrupolar chromophores play a critical role in observed the two-photon absorption (2PA) cross-section for an intramolecular charge transfer (ICT) state interaction in the multibranched quadrupolar chromophores.

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Enhanced Two‐Photon Absorption of Organic Chromophores: Theoretical and Experimental Assessments

Cited by 535 publications

References 321 publications

Comparison of Carbazole and Fluorene Donating Effects on the Two‐Photon Absorption and Nitric Oxide Photorelease Capabilities of a Ruthenium–Nitrosyl Complex

Comparison of Carbazole and Fluorene Donating Effects on the Two‐Photon Absorption and Nitric Oxide Photorelease Capabilities of a Ruthenium–Nitrosyl Complex

Intermolecular charge transfer enhances two-photon absorption in yellow fluorescent protein

Localized Emitting State and Energy Transfer Properties of Quadrupolar Chromophores and (Multi)Branched Derivatives

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