Phenylene Vinylene Platinum(II) Acetylides with Prodigious Two-Photon Absorption

Dubinina, Galyna G.; Price, Randi S.; Abboud, Khalil A.; Wicks, Geoffrey; Wnuk, Paweł; Stepanenko, Yuriy; Drobizhev, Mikhail; Rebane, Aleksander; Schanze, Kirk S.

doi:10.1021/ja309393c

Cited by 86 publications

(115 citation statements)

References 16 publications

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“…Bis‐diphenylaminostilbene (bDPAS) diluted in dichloromethane was used as the reference standard for the 2PEF measurements . When the fluorescence quantum yields were too low for reliable 2PEF measurements, the femtosecond NLT method was used to determine the 2PA cross‐sections in a range of 570–800 nm . Briefly, for the NLT measurements, the same laser setup was employed, but the pulse repetition rate was reduced to 100 Hz.…”

Section: Methodsmentioning

confidence: 99%

“…[35] When the fluorescence quantum yields were too low for reliable 2PEF measurements, the femtosecond NLTm ethod was used to determine the 2PAc ross-sections in ar ange of 570-800 nm. [36] Briefly,f or the NLT measurements, the same laser setup was employed, but the pulse repetition rate was reduced to 100 Hz. The 1PAb eam was additionally collimated using as eries of apertures and lenses.…”

Section: Synthesis Of Compound (8)mentioning

confidence: 99%

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Symmetry Breaking in Pyrrolo[3,2‐b]pyrroles: Synthesis, Solvatofluorochromism and Two‐photon Absorption

Łukasiewicz

Ryu

Mikhaylov

et al. 2017

Chemistry An Asian Journal

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Five centrosymmetric and one dipolar pyrrolo[3,2-b]pyrroles, possessing either two or one strongly electron-withdrawing nitro group have been synthesized in a straightforward manner from simple building blocks. For the symmetric compounds, the nitroaryl groups induced spontaneous breaking of inversion symmetry in the excited state, thereby leading to large solvatofluorochromism. To study the origin of this effect, the series employed peripheral structural motifs that control the degree of conjugation via altering of dihedral angle between the 4-nitrophenyl moiety and the electron-rich core. We observed that for compounds with a larger dihedral angle, the fluorescence quantum yield decreased quickly when exposed to even moderately polar solvents. Reducing the dihedral angle (i.e., placing the nitrobenzene moiety in the same plane as the rest of the molecule) moderated the dependence on solvent polarity so that the dye exhibited significant emission, even in THF. To investigate at what stage the symmetry breaking occurs, we measured two-photon absorption (2PA) spectra and 2PA cross-sections (σ ) for all six compounds. The 2PA transition profile of the dipolar pyrrolo[3,2-b]pyrrole, followed the corresponding one-photon absorption (1PA) spectrum, which provided an estimate of the change of the permanent electric dipole upon transition, ≈18 D. The nominally symmetric compounds displayed an allowed 2PA transition in the wavelength range of 700-900 nm. The expansion via a triple bond resulted in the largest peak value, σ =770 GM, whereas altering the dihedral angle had no effect other than reducing the peak value two- or even three-fold. In the S →S transition region, the symmetric structures also showed a partial overlap between 2PA and 1PA transitions in the long-wavelength wing of the band, from which a tentative, relatively small dipole moment change, 2-7 D, was deduced, thus suggesting that some small symmetry breaking may be possible in the ground state, even before major symmetry breaking occurs in the excited state.

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Section: Methodsmentioning

confidence: 99%

Section: Synthesis Of Compound (8)mentioning

confidence: 99%

Symmetry Breaking in Pyrrolo[3,2‐b]pyrroles: Synthesis, Solvatofluorochromism and Two‐photon Absorption

Łukasiewicz

Ryu

Mikhaylov

et al. 2017

Chemistry An Asian Journal

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“…The principle of the NLT measurement was described in ref 30. Briefly, the OPA beam was passed through the sample and the transmittance T, defined as the ratio of the relative pulse energy after and before the sample was measured with two photodetectors (Photodetectrors #1 and #2 in Figure 2, DET100A, Thorlabs) and a DAQ board (PCI-6110, National Instruments).…”

Section: Methodsmentioning

confidence: 99%

Symmetry Breaking in Platinum Acetylide Chromophores Studied by Femtosecond Two-Photon Absorption Spectroscopy

et al. 2014

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We study instantaneous two-photon absorption (2PA) in a series of nominally quasi-centrosymmetric trans-bis(tributylphosphine)-bis-(4-((9,9-diethyl-7-ethynyl-9H-fluoren-2-yl) ethynyl)-R)-platinum complexes, where 11 different substituents, R = N(phenyl)(NPh), NH, OCH, t-butyl, CH, H, F, CF, CN, benzothiazole, and NO, represent a range of electron-donating (ED) and electron-withdrawing (EW) strengths, while the Pt core acts as a weak ED group. We measure the 2PA cross section in the 540-810 nm excitation wavelength range by complementary femtosecond two-photon excited fluorescence (2PEF) and nonlinear transmission (NLT) methods and compare the obtained values to those of the Pt-core chromophore and the corresponding noncentrosymmetric side group (ligand) chromophores. Peak 2PA cross sections of neutral and ED-substituted Pt complexes occur at S → S transitions to higher energy states, above the lowest-energy S → S transition, and the corresponding values increase systematically with increasing ED strength, reaching maximum value, σ ∼ 300 GM (1 GM = 10 cm s), for R = NPh. At transition energies overlapping with the lowest-energy S → S transition in the one-photon absorption (1PA) spectrum, the same neutral and ED-substituted Pt complexes show weak 2PA, σ < 30-100 GM, which is in agreement with the nearly quadrupolar structure of these systems. Surprisingly, EW-substituted Pt complexes display a very different behavior, where the peak 2PA of the S → S transition gradually increases with increasing EW strength, reaching values σ = 700 GM for R = NO, while in the S → S transition region the peak 2PEF cross section decreases. We explained this effect by breaking of inversion symmetry due to conformational distortions associated with low energy barrier for ground-state rotation of the ligands. Our findings are corroborated by theoretical calculations that show large increase of the permanent electric dipole moment change in the S → S transition when ligands with strong EW substituents are twisted by 90° relative to the planar chromophore. Our NLT results in the S → S transition region are quantitatively similar to those obtained from the 2PEF measurement. However, at higher transition energy corresponding to S → S transition region, the NLT method yields effective multiphoton absorption stronger than the 2PEF measurement in the same systems. Such enhancement is observed in all Pt complexes as well as in all ligand chromophores studied, and we tentatively attribute this effect to nearly saturated excited-state absorption (ESA), which may occur if 2PA from the ground state is immediately followed by strongly allowed 1PA to higher excited states.

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“…Note the remarkably good correspondence between the 2PA spectra measured in monoliths and the values obtained in THF solution for the same complexes. 26 In the shorter wavelength region, < 600 nm, the 2PA cross section values of the monoliths are slightly higher than that in the solutions suggesting that in the solid environment S 1 −S n singlet excited state absorption may have a larger contribution than in solution, likely due to slower vibrational relaxation in the solid state. Most importantly for the OPL application, the exceptional spectral overlap between the 2PA and the triplet−triplet excited state absorption is retained in the PMMA host.…”

Section: ■ Introductionmentioning

confidence: 87%

“…Two photon absorption (2PA) spectra and cross sections (σ 2 ) of the monoliths were obtained with good accuracy using the collimated-beam femtosecond nonlinear transmission method. 26 The 2PA spectra and cross-section values for the TPV1, crossTPV1, and crossTPV3 doped monoliths were measured and compared to those previously reported for THF solutions of the complexes (Figure 7). The 2PA cross sections for the monoliths were calculated based on the estimated chromophore concentrations listed in Table 2.…”

Section: ■ Introductionmentioning

confidence: 99%

Polymer Monoliths Containing Two-Photon Absorbing Phenylenevinylene Platinum(II) Acetylide Chromophores for Optical Power Limiting

Price

Dubinina

Wicks

et al. 2015

ACS Appl. Mater. Interfaces

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A series of platinum(II) acetylide complexes containing p-phenylenevinylene and moieties end-capped with triphenylamine groups have been incorporated into poly(methyl methacrylate) (PMMA) monoliths for optical power limiting applications. The one- and two-photon photophysical properties were investigated and compared to the photophysical properties in THF. The absolute two-photon absorption cross-section values for the monolith samples were measured and are comparable to the values obtained in solution. In the PMMA monoliths, the complexes retained the important two-photon absorption and reverse saturable absorption properties necessary for optical power limiting via dual mode mechanism, and their strong nonlinear absorption property was demonstrated by the open-aperture Z-scan method. Photostability studies of the p-phenylenevinylene platinum(II) acetylide complexes showed two photodegradation processes: a trans-to-cis isomerization and a singlet-oxygen sensitized self-oxidative cleavage. The photostability of the least photostable complex TPV0 was increased upon incorporation into a PMMA matrix.

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Phenylene Vinylene Platinum(II) Acetylides with Prodigious Two-Photon Absorption

Cited by 86 publications

References 16 publications

Symmetry Breaking in Pyrrolo[3,2‐b]pyrroles: Synthesis, Solvatofluorochromism and Two‐photon Absorption

Symmetry Breaking in Pyrrolo[3,2‐b]pyrroles: Synthesis, Solvatofluorochromism and Two‐photon Absorption

Symmetry Breaking in Platinum Acetylide Chromophores Studied by Femtosecond Two-Photon Absorption Spectroscopy

Polymer Monoliths Containing Two-Photon Absorbing Phenylenevinylene Platinum(II) Acetylide Chromophores for Optical Power Limiting

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