Ruthenium(II)-nitrosyl polypyridinyl Complexes: from NO/ON Isomerization to NO delivery

2015 ◽  
Vol 1767 ◽  
pp. 65-74
Author(s):  
Pascal G. Lacroix ◽  
Isabelle Malfant
Keyword(s):  
Solid State ◽  
Photon Absorption ◽  
High Yield ◽  
Absorption Process ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Ruthenium Nitrosyl ◽  
Nlo Response ◽  
No Release ◽  
Computational Strategy

ABSTRACTRuthenium-nitrosyl (RuII(NO)) complexes are stable in the dark, but exhibit a unique photoreactivity which can lead either to a solid state isomerization from RuII(NO) to RuII(ON), or to a nitric oxide (NO·) release in solution. From our recent discovery of a high yield of isomerization (> 92%) in [RuII(py)4Cl(NO)](PF6)2, we have developed a computational strategy aimed at designing switchable nonlinear optical (NLO) material with high contrast (large difference in the on / off NLO response) in the solid state. Our synthetic targets are terpyridine based RuII chromophores in which various substituents can be introduced to adjust the NLO response which, at best, should be vanishing in the off state. Alternatively, these complexes can undergo a photo-induced NO· release in solution, a possibility which becomes increasingly appealing in relation to the discovery of the numerous biological roles of NO·, in the context of the emergence of the photodynamic therapy. A promising fluorene-terpyridine RuII(NO) complex was investigated, which could find an additional interest in relation to its capability for releasing NO· by a two-photon absorption process.

scholarly journals Tuning of Hyperpolarizability, One- and Two-Photon Absorption of D-A and D-A-A Type Intramolecular Charge Transfer Based Sensors

2019 ◽  
Author(s):  
Pralok K. Samanta ◽  
Md Mehboob Alam ◽  
Ramprasad Misra ◽  
Swapan K. Pati
Keyword(s):  
Charge Transfer ◽  
Gas Phase ◽  
Density Functional ◽  
Intramolecular Charge Transfer ◽  
Photon Absorption ◽  
First Hyperpolarizability ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Nlo Response ◽  
Donor Acceptor

Solvents play an important role in shaping the intramolecular charge transfer (ICT) properties of π-conjugated molecules, which in turn can affect their one-photon absorption (OPA) and two-photon absorption (TPA) as well as the static (hyper)polarizabilities. Here, we study the effect of solvent and donor-acceptor arrangement on linear and nonlinear optical (NLO) response properties of two novel ICT-based fluorescent sensors, one consisting of hemicyanine and dimethylaniline as electron withdrawing and donating groups (molecule 1), respectively and its boron-dipyrromethene (BODIPY, molecule 2)-fused counterpart (molecule 3). Density functional theoretical (DFT) calculations using long-range corrected CAM-B3LYP and M06-2X functionals, suitable for studying properties of ICT molecules, are employed to calculate the desired properties. The dipole moment (µ) as well as the total first hyperpolarizability (β<sub>total</sub>) of the studied molecules in the gas phase is dominantly dictated by the component in the direction of charge transfer. The ratios of vector component of first hyperpolarizability (β<sub>vec</sub>) to β<sub>total</sub> also reveal unidirectional charge transfer process. The properties of the medium significantly affect the OPA, hyperpolarizability and TPA properties of the studied molecules. Time dependent DFT (TDDFT) calculations suggest interchanging between two lowest excited states of molecule 3 from the gas phase to salvation. The direction of charge polarization and dominant transitions among molecular orbitals involved in the OPA and TPA processes are studied. The results presented are expected to be useful in tuning the NLO response of many ICT-based chromophores, especially those with BODIPY acceptors.<br>

scholarly journals Nonlinear Optical Pigments. Two-Photon Absorption in Crosslinked Conjugated Polymers and Prospects for Remote Nonlinear Optical Thermometry

Polymers ◽  
2020 ◽  
Vol 12 (8) ◽  
pp. 1670
Author(s):  
Jan K. Zaręba ◽  
Marcin Nyk ◽  
Marek Samoć
Keyword(s):  
Solid State ◽  
Conjugated Polymers ◽  
Nonlinear Optical ◽  
Photon Absorption ◽  
Model Compounds ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Sensing Applications ◽  
Spectrally Resolved ◽  
The Impact

Nonlinear optical (NLO) pigments are compounds insoluble in solvents that exhibit phenomena related to nonlinear optical susceptibilities (χ(n) where n = 2,3,...), e.g., two-photon absorption (2PA) which is related to the imaginary part of χ(3). Determination of spectrally-resolved 2PA properties for NLO pigments of macromolecular nature, such as coordination polymers or crosslinked polymers, has long been a challenging issue due to their particulate form, precluding characterizations with standard techniques such as Z-scan. In this contribution, we investigate thus far unknown spectrally-resolved 2PA properties of a new subclass of NLO pigments—crosslinked conjugated polymers. The studied compounds are built up from electron-donating (triphenylamine) and electron-withdrawing (2,2’-bipyridine) structural fragments joined by vinylene (Pol1) or vinyl(4-ethynylphenyl) (Pol2) aromatic bridges. 2PA properties of these polymers have been characterized in broad spectral range by specially modified two-photon excited fluorescence (TPEF) techniques: solid state TPEF (SSTPEF) and internal standard TPEF (ISTPEF). The impact of self-aggregation of aromatic backbones on the 2PA properties of the polymers has been evaluated through extended comparisons of NLO parameters, i.e., 2PA cross sections (σ2) and molar-mass normalized 2PA merit factors (σ2/M) with those of small-molecular model compounds: Mod1 and Mod2. By doing this, we found that the 2PA response of Pol1 and Pol2 is improved 2–3 times versus respective model compounds in the solid state form. Further comparisons with 2PA results collected for diluted solutions of Mod1 and Mod2 supports the notion that self-aggregated structure contributes to the observed enhancement of 2PA response. On the other hand, it is clear that Pol1 and Pol2 suffer from aggregation-caused quenching phenomenon, well reflected in time-resolved fluorescence properties as well as in relatively low values of quantum yield of fluorescence. Accordingly, despite improved intrinsic 2PA response, the effective intensity of two-photon excited emission for Pol1 and Pol2 is slightly lower relative to Mod1 and Mod2. Finally, we explore temperature-resolved luminescence properties under one- (377 nm), two- (820 nm), and three-photon excitation (1020 nm) conditions of postsynthetically Eu3+-functionalized material, Pol1-Eu, and discuss its suitability for temperature sensing applications.

scholarly journals Photolysis of SiH4 by the Third Harmonic of a Nd:YAG Laser at 355 NM

1996 ◽  
Vol 16 (4) ◽  
pp. 245-253
Author(s):  
K. Sentrayan ◽  
E. Haque ◽  
A. Michael ◽  
V. S. Kushawaha
Keyword(s):  
Laser Energy ◽  
Emission Spectra ◽  
Photon Absorption ◽  
Absorption Process ◽  
Third Harmonic ◽  
Two Photon Absorption ◽  
Two Photon ◽  
The Third ◽  
Atomic Lines ◽  
White Deposit

The photolysis of silane (SiH4) was carried out using the third harmonic of a Nd: YAG laser at 355 nm, at a fixed SiH4 pressure of 350 Torr, varying the laser energy fluence in the range of 30–300 Jcm-2. The emission spectra indicates that the photofragments formed are SiH2, SiH, Si, H2, and H. The (A1B1-X1A1) transitions at 552.7 nm, 525.3 nm, 505.6 nm, and 484.7 nm of SiH2 are due to a two photon absorption process. The (A2Δ-X2π) transitions of SiH at 425.9 nm, 418 nm, 414.2 nm, 412.8 nm and 395.6 nm are due to a three photon absorption process. The brownish white deposit on the cell windows indicates the presence of amorphous silicon (a:Si-H). The two atomic lines of Si(4s1P0→ 3p21D2) at 288.1 nm, and (4s3Pj→ 3P3Pj) at 251.6 nm are observed. The atomic Si transitions are due to a three photon absorption. We observed seven transitions due to molecular hydrogen at wavelengths 577.5 nm, 565.5 nm, 534.4 nm, 542.5 nm, 471 nm, 461.7 nm, and 455.4 nm. These bands are due to a four photon absorption proc6ss. In addition to the molecular bands we also observed hydrogen atomic lines Hβ, Hγ and Hδ.

scholarly journals Determination of 4H-SiC Ionization Rates Using OBIC Based on Two-Photon Absorption

2016 ◽  
Vol 858 ◽  
pp. 245-248 ◽  
Author(s):  
Hassan Hamad ◽  
Christophe Raynaud ◽  
Pascal Bevilacqua ◽  
Sigo Scharnholz ◽  
Bertrand Vergne ◽  
...  
Keyword(s):  
Single Photon ◽  
Green Laser ◽  
Photon Absorption ◽  
Absorption Process ◽  
Field Range ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Avalanche Diodes ◽  
Single Photon Absorption ◽  
Ionization Rates

Optical Beam Induced Current (OBIC) measurements are performed on 4H-SiC avalanche diodes with a very thin and a highly doped active region. A pulsed green laser, with a wavelength of 532 nm, illuminates a reverse biased diode leading to generate electron-hole pairs in the space charge region. Comparison between the 4H-SiC bandgap and the incident photon energy shows that single photon absorption process can be neglected and two-photon absorption process dominates in this case. Ionization rates are then extracted from multiplication curve in a high electric field range (3 to 5 MV.cm–1). Results are in good agreement with previous ones obtained on the same diodes using single photon absorption process.

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