Drastic enhancement of two-photon absorption in porphyrins associated with symmetrical electron-accepting substitution

Drobizhev, Mikhail; Karotki, Aliaksandr; Kruk, M. M.; Мамардашвили, Н. Ж.; Rebane, Aleksander

doi:10.1016/s0009-2614(02)00999-5

Cited by 101 publications

(99 citation statements)

References 24 publications

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“…Lately, attention has turned toward multipolar [22][23][24][25][26][27][28][29][30][31][32][33] and branched structures including dendrimers. 23,24,28,[33][34][35][36][37][38][39][40][41][42][43] Given the huge synthetic effort needed to build such supramolecular structures, a detailed understanding of the effect of branching of molecular entities on the linear and nonlinear optical properties is of major interest. Thus, further development of approaches for rational design of NLO assemblies is needed in order to focus the synthesis on knowledgebased materials.…”

Section: Introductionmentioning

confidence: 99%

Effects of (Multi)branching of Dipolar Chromophores on Photophysical Properties and Two-Photon Absorption

et al. 2005

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To investigate the effect of branching on linear and nonlinear optical properties, a specific series of chromophores, epitome of (multi)branched dipoles, has been thoroughly explored by a combined theoretical and experimental approach. Excited-state structure calculations based on quantum-chemical techniques (timedependent density functional theory) as well as a Frenkel exciton model nicely complement experimental photoluminescence and one-and two-photon absorption findings and contribute to their interpretation. This allowed us to get a deep insight into the nature of fundamental excited-state dynamics and the nonlinear optical (NLO) response involved. Both experiment and theory reveal that a multidimensional intramolecular charge transfer takes place from the donating moiety to the periphery of the branched molecules upon excitation, while fluorescence stems from an excited state localized on one of the dipolar branches. Branching is also observed to lead to cooperative enhancement of two-photon absorption (TPA) while maintaining high fluorescence quantum yield, thanks to localization of the emitting state. The comparison between results obtained in the Frenkel exciton scheme and ab initio results suggests the coherent coupling between branches as one of the possible mechanisms for the observed enhancement. New strategies for the rational design of NLO molecular assemblies are thus inferred on the basis of the acquired insights.

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Section: Introductionmentioning

confidence: 99%

Effects of (Multi)branching of Dipolar Chromophores on Photophysical Properties and Two-Photon Absorption

et al. 2005

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“…Rebane [17,18], and Cramb [19] reported monomeric porphyrin derivatives with relatively large σ (2) values (Scheme 3). We reported porphyrin tetramers, composing of two butadiyne-linked porphyrin dimers, which were self-assembled by zinc to imidazolyl axial coordination, with a large value of 7600 GM employing femtosecond pulses at 870 nm (Scheme 4, top) [20,21].…”

Section: Scheme 2 Dendritic Two-photon Absorbing Moleculesmentioning

confidence: 99%

Two-Photon Absorbing Molecules as Potential Materials for 3D Optical Memory

Ogawa

2014

Applied Sciences

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Abstract:In this review, recent advances in two-photon absorbing photochromic molecules, as potential materials for 3D optical memory, are presented. The investigations introduced in this review indicate that 3D data storage processing at the molecular level is possible. As 3D memory using two-photon absorption allows advantages over existing systems, the use of two-photon absorbing photochromic molecules is preferable. Although there are some photochromic molecules with good properties for memory, in most cases, the two-photon absorption efficiency is not high. Photochromic molecules with high two-photon absorption efficiency are desired. Recently, molecules having much larger two-photon absorption cross sections over 10,000 GM (GM= 10 ) have been discovered and are expected to open the way to realize two-photon absorption 3D data storage.

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“…[5][6][7][8] These molecules are very attractive for applications based on nonlinear absorption, such as optical power limiting, 9,10 high-density volumetric data storage, 11,12 and deep tissue photodynamic therapy. 13,14 We have recently studied the 2PA spectra of a series of symmetrically substituted Pcs, and found strong, gerade-gerade (g-g) 2PA transitions in the energy region between the Q-and B-bands.…”

Section: Introductionmentioning

confidence: 99%

Alternative selection rules for one- and two-photon transitions in tribenzotetraazachlorin: Quasi-centrosymmetrical π-conjugation pathway of formally non-centrosymmetrical molecule

Makarov

Drobizhev

Wicks

et al. 2013

The Journal of Chemical Physics

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We compare the two-photon absorption (2PA) spectra of non-centrosymmetrical metal-free tribenzotetraazachlorin (H 2 TBTAC) and analogous symmetrical tetra-tert-butyl-phthalocyanine (H 2 TtBuPc). Surprisingly, despite formal lack of center of inversion, the 2PA spectrum of H 2 TBTAC displays a two-photon allowed transition at 935 nm, similar to gerade-gerade (g-g) transitions observed in H 2 TtBuPc and in other symmetrical phthalocyanines. This transition is even better resolved in the singlet-singlet excited-state absorption spectrum. We tentatively explain the survival of the g-g transition in H 2 TBTAC by assuming that the main π -electron conjugation pathway in the tetraazasubstituted tetrapyrrole macrocycle bypasses the outer parts of the two oppositely located isoindole rings and thus renders the optically responsive core of the chromophore quasi-centrosymmetrical. By using the independently measured ground-and excited-state absorption extinction coefficients, we also show that the two-photon absorptivity can be quantitatively explained by a simple threelevel model with the lowest energy Q 1 state serving as an intermediate level.

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Drastic enhancement of two-photon absorption in porphyrins associated with symmetrical electron-accepting substitution

Cited by 101 publications

References 24 publications

Effects of (Multi)branching of Dipolar Chromophores on Photophysical Properties and Two-Photon Absorption

Effects of (Multi)branching of Dipolar Chromophores on Photophysical Properties and Two-Photon Absorption

Two-Photon Absorbing Molecules as Potential Materials for 3D Optical Memory

Alternative selection rules for one- and two-photon transitions in tribenzotetraazachlorin: Quasi-centrosymmetrical π-conjugation pathway of formally non-centrosymmetrical molecule

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