Organometallic Complexes for Non-Linear Optics. 59. Syntheses and Optical Properties of Some Octupolar (N-Heterocyclic Carbene)gold Complexes

2017 ◽  
Vol 70 (1) ◽  
pp. 79 ◽  
Author(s):  
Gang Liu ◽  
Cristóbal Quintana ◽  
Genmiao Wang ◽  
Mahesh S. Kodikara ◽  
Jun Du ◽  
...  
Keyword(s):  
Optical Properties ◽  
Rayleigh Scattering ◽  
Second Harmonic ◽  
Organometallic Complexes ◽  
Low Energy ◽  
Oscillator Strengths ◽  
Linear Optics ◽  
Energy Bands ◽  
Nanosecond Pulses ◽  
Energy Transitions

The syntheses of octupolar alkynes 1,3,5-{4-(4-HC≡CC6H4-1-C≡C)-3,5-Et2C6H2-1-C≡C}3C6H3 (4) and 1,3,5-{4-(4-HC≡CC6H4-1-C≡C-4-C6H4-1-C≡C)-3,5-Et2C6H2-1-C≡C}3C6H3 (6), diphenylamino-substituted 1,3,5-(4-Ph2NC6H4-1-C≡C)3C6H3 (7), 1,3,5-(4-Ph2NC6H4-1-C≡C-4-C6H4-1-C≡C)3C6H3 (8), 1,3,5-{4-(4-Ph2NC6H4-1-C≡C-4-C6H4-1-C≡C)-3,5-Et2C6H2-1-C≡C}3C6H3 (9), and 1,3,5-{4-(4-Ph2NC6H4-1-C≡C-4-C6H4-1-C≡C-4-C6H4-1-C≡C)-3,5-Et2C6H2-1-C≡C}3C6H3 (10), and (N-heterocyclic carbene)gold-appended 1,3,5-{[(NHC-iPr)Au]C≡C}3C6H3 (11), 1,3,5-{[(NHC-iPr)Au]C≡C-4-C6H4-1-C≡C}3C6H3 (12), 1,3,5-{4-([(NHC-iPr)Au]C≡C-4-C6H4-1-C≡C)-3,5-Et2C6H2-1-C≡C}3C6H3 (13), and 1,3,5-{4-([(NHC-iPr)Au]C≡C-4-C6H4-1-C≡C-4-C6H4-1-C≡C)-3,5-Et2C6H2-1-C≡C}3C6H3 (14) [NHC-iPr = κC-cyclo-CN(2,6-C6H3iPr2)CH=CHN(2,6-C6H3iPr2)] are reported. The low-energy bands in the linear optical absorption spectra of all three sets of compounds are red-shifted and increase in intensity upon π-delocalizable ‘arm’ lengthening. The diphenylamino- and (NHC-iPr)gold-terminated compounds do not exhibit measurable second-harmonic generation as assessed by hyper-Rayleigh scattering at 1064 nm using nanosecond pulses. Computational studies have been employed to rationalize the optical properties of the new compounds. Calculations on 7–10 reveal that the lowest-energy transitions with large oscillator strengths are predominantly [Ph2NC6H4] (π) → [arms + core] (π*) in character, whereas calculations on 11–14 suggest that the low-energy transitions relate to the transfer of electron density from the Au-alkynyl core group to the terminal NHC groups.

Organometallic Complexes for Non-Linear Optics. 51. Second- and Third-Order Non-Linear Optical Properties of Alkynylgold Complexes

2012 ◽  
Vol 65 (7) ◽  
pp. 834 ◽  
Author(s):  
Adam Barlow ◽  
Bandar Babgi ◽  
Marek Samoc ◽  
T. Christopher Corkery ◽  
Stijn van Cleuvenbergen ◽  
...  
Keyword(s):  
Optical Properties ◽  
Rayleigh Scattering ◽  
Organometallic Complexes ◽  
Photon Absorption ◽  
Imaginary Component ◽  
Linear Optics ◽  
Non Linear Optics ◽  
Non Linear ◽  
Linear Optical Properties ◽  
Linear Optical

The alkynes HC≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2 (4) and HC≡CC6H4-4-C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2 (6) and gold alkynyl complexes Au{C≡CC6H2-2,5-(OEt)2-4-C≡CC6H4-4-NO2}(PPh3) (7), Au(C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2)(PPh3) (8), and Au(C≡CC6H4-4-C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2)(PPh3) (9) have been synthesized. The linear optical properties and quadratic optical non-linearities of 7–9 have been measured, the latter by hyper-Rayleigh scattering at 1064 nm, and compared with data for the previously reported complexes Au(C≡CC6H4-4-NO2)(PPh3) (10) and Au(C≡CC6H4-4-C≡CC6H4-4-NO2)(PPh3) (11). The optical absorption maximum red-shifts and the first hyperpolarizabilities increase on π-system lengthening and on introduction of electron-releasing substituents on the π-bridge ring adjacent to the metal centre. The cubic non-linear optical properties of 1,4-{(PCy3)Au(C≡C)}2C6H4 (12) and {(PCy3)Au(C≡C-4-C6H4C≡C)}6C6 (13) have been assessed by wide spectroscopic range femtosecond Z-scan studies; the maximal values of the imaginary component and the effective two-photon absorption cross-section increase markedly on proceeding from linear complex 12 to 6-fold-symmetric complex 13, an increase that is maintained when data are scaled by relative molecular weight.

scholarly journals L-alaninium perrhenate: crystal structure and non-linear optical properties

2014 ◽  
Vol 12 (10) ◽  
pp. 1016-1022 ◽  
Author(s):  
Vitor Rodrigues ◽  
Maria Costa ◽  
Etelvina Gomes ◽  
Dmitry Isakov ◽  
Michael Belsley
Keyword(s):  
Crystal Structure ◽  
Optical Properties ◽  
Second Harmonic ◽  
Negative Ions ◽  
Damage Threshold ◽  
Linear Optics ◽  
Second Harmonic Generation Efficiency ◽  
Non Linear ◽  
Linear Optical Properties ◽  
Linear Optical

AbstractThe crystal structure and non-linear optical properties of L-alaninium perrhenate, C3H8NO2+ ReO4 −, are reported. The protonated amino acid and the perrhenate anion have their usual geometries. The three-dimensional hydrogen-bonded network can be seen as a stacking of layers parallel to the (100) planes. Each layer is formed by chains of alternating positive and negative ions along the b and c axes. Hydrogen bonding of adjacent layers forms alternating chains along the a axis. A high damage threshold and a second-harmonic generation efficiency three times that of KDP make this new material potentially useful in non-linear optics.

scholarly journals Propiedades ópticas no lineales del difosfaferroceno. Un estudio teórico

2018 ◽  
Vol 3 (3) ◽  
pp. 11
Author(s):  
Johan Urdaneta ◽  
Humberto Soscún ◽  
Ana Ocando ◽  
Alberto Campos
Keyword(s):  
Optical Properties ◽  
Dft Method ◽  
Organometallic Complexes ◽  
Experimental Comparison ◽  
Potential Candidate ◽  
Linear Optics ◽  
Electronic Density ◽  
Non Linear Optics ◽  
Basic Set ◽  
Nlo Materials

  La óptica no lineal (NLO, por sus siglas en inglés de: No Linear Optics) se ha desarrollado en los últimos años como un importante campo de investigación debido a su aplicabilidad en la fotoelectrónica y tecnología fotónica. En las últimas décadas los complejos organometálicos se han convertido en una clase de moléculas de gran interés en NLO. Estos complejos combinan las ventajas de las moléculas orgánicas con las ofrecidas por las sales inorgánicas. En este trabajo se realizó un estudio mecano-cuántico computacional de la contribución electrónica en fase gas de las propiedades ópticas del difosfaferroceno a nivel estático, empleando el método DFT CAM-B3LYP y el conjunto base 6-31+G(d,p), en conjunto con la metodología de campo finito basadas en la ecuaciones de Kurtz. Adicionalmente se realizaron cálculos para el ferroceno a modo comparativo. La comparación teoría-experimentales, muestra que la metodología empleada proporciona valores comparables, mostrando una correspondencia de 93 % para aave, y un 87 % para gave. Con respecto a las propiedades ópticas, se observa que el complejo de difosfaferroceno es mayormente polarizable que el ferroceno. Sin embargo, las mayores contribuciones se observan en las propiedades NLO, donde para b la respuesta calculada para el complejo difosfaferroceno es 72 ua, a diferencia de ferroceno el cual no presenta respuesta por ser una molécula centro simétrica. En gave, la respuesta es casi dos veces superior. Estos resultados permiten inferir que la interacción de anillos fosfolil con el átomo de Fe origina una mayor perturbación o deslocalización de la densidad electrónica de la molécula, promoviendo así elevadas respuestas ópticas cuando se aplican campos eléctricos, catalogándolo como un candidato potencial para el diseño de nuevos materiales NLO.   Palabras clave: NLO, difosfaferroceno, óptica, DFT, (hiper)polarizabilidades.   Abstract Non linear optics (NLO) has been developed in recent years as an important field of research due to its applicability in photoelectronics and photonic technology. In recent decades organometallic complexes have become a class of molecules of great interest in NLO. These complexes combine the advantages of organic molecules with the ones offered by inorganic salts. In this work, a computational quantum mechanics study of the electronic contribution in gas phase of the optical properties of diphosphaferrocene at a static level was carried out, using the CAM-B3LYP DFT Method and the 6-31+G(d,p) basic set, together with the finite field methodology based on Kurtz equations. Additionally, the ferrocene molecule was studied for comparison purposes. The theory-experimental comparison shows that the methodology used provides comparable values, showing a 93% correspondence for aave, and 87% for gave. With respect to the optical properties, it is observed that the diphosphaferrocene complex is mostly more polarizable than ferrocene. However, the greatest contributions are observed in the NLO properties, where for b, the calculated response for the diphosphaferrocene complex is 72 ua, different from, which does not respond because it is a symmetric center molecule. In gave, the answer is almost double. These results allow us to infer that the interaction of phospholyl rings with the Fe atom causes a greater perturbation or delocalization of the electronic density of the molecule, promoting high optical responses when an electric field is applied, cataloging it as a potential candidate for the design of new NLO materials.   Key words: NLO, diphosphaferrocene, optics, DFT, (hyper) polarizabilities.

scholarly journals Study of the hyper-Rayleigh scattering first hyperpolarizability of a chalcone derivative in various solvent media

2019 ◽  
Vol 11 (4) ◽  
pp. 96
Author(s):  
Adailton N. De Castro ◽  
Loyanne C. P. Da Silva ◽  
Francisco A. P. Osório ◽  
Basilio Baseia ◽  
Clodoaldo Valverde
Keyword(s):  
Optical Properties ◽  
Nonlinear Optical ◽  
Rayleigh Scattering ◽  
Second Harmonic ◽  
Chem Phys ◽  
Nonlinear Optical Properties ◽  
Optical Material ◽  
Nonlinear Optical Material ◽  
Third Order ◽  
Optical Effects

In this work we investigate the solvent media effects on the nonlinear optical properties of a chalcone derivative, (2E)-3-(3-methylphenyl)-1-(4-nitrophenyl) prop-2-en-1-one (3MPNP), using the polarizable continuum model (PCM) at DFT/B3LYP/6-311+G(d) level. The behavior of the hyper-Rayleigh scattering first hyperpolarizability and the average second hyperpolarizability, are studied as function of the dielectric constant of the solvent medium in both dynamic and static cases. Full Text: PDF ReferencesL. R. Almeida et al., "Synthesis, structural characterization and computational study of a novel amino chalcone: a potential nonlinear optical material", New J. Chem., vol. 41, no. 4, pp. 1744-1754, 2017. CrossRef P. K. Murthy et al., "An analysis of structural and spectroscopic signatures, the reactivity study of synthetized 4,6-dichloro-2-(methylsulfonyl)pyrimidine: A potential third-order nonlinear optical material", J. Mol. Struct., vol. 1186, pp. 263-275, Jun. 2019. CrossRef J. Kongsted, A. Osted, K. V Mikkelsen, and O. Christiansen, "“Second harmonic generation second hyperpolarizability of water calculated using the combined coupled cluster dielectric continuum or different molecular mechanics methods", J. Chem. Phys., vol. 120, no. 8, pp. 3787-98, Feb. 2004. CrossRef T. L. Fonseca, J. R. Sabino, M. A. Castro, and H. C. Georg, "A theoretical investigation of electric properties of L-arginine phosphate monohydrate including environment polarization effects", J. Chem. Phys., vol. 133, no. 14, pp. 1-8, 2010. CrossRef A. KARAKAŞ, Z. E. KOÇ, M. FRIDRICHOVÁ, P. NĚMEC, and J. KROUPA, "THE INVESTIGATION OF SECOND-ORDER NONLINEAR OPTICAL PROPERTIES OF P-NITROPHENYLAZOANILINE: SECOND HARMONIC GENERATION AND AB INITIO COMPUTATIONS", J. Theor. Comput. Chem., vol. 11, no. 01, pp. 209-221, Feb. 2012. CrossRef T. Seidler, K. Stadnicka, and B. Champagne, "Second‐order Nonlinear Optical Susceptibilities and Refractive Indices of Organic Crystals from a Multiscale Numerical Simulation Approach", Adv. Opt. Mater., vol. 2, no. 10, pp. 1000-1006, Oct. 2014. CrossRef L. M. G. Abegão et al., "Second- and third-order nonlinear optical properties of unsubstituted and mono-substituted chalcones", Chem. Phys. Lett., vol. 648, pp. 91-96, Mar. 2016. CrossRef W. F. Vaz et al., "Synthesis, characterization, and third-order nonlinear optical properties of a new neolignane analogue", RSC Adv., vol. 6, no. 82, pp. 79215-79227, 2016. CrossRef C. Valverde et al., "The solid state structure and environmental polarization effect of a novel asymmetric azine", New J. Chem., vol. 41, no. 19, pp. 11361-11371, 2017. CrossRef P. N. Prasad, D. J. Williams, and others, Introduction to nonlinear optical effects in molecules and polymers, vol. 1. Wiley New York etc., 1991. DirectLink P. Günter, Nonlinear Optical Effects and Materials, 4th ed. Berlin: Springer Berlin Heidelberg, 2000. CrossRef H. Inan et al., "Photonic crystals: emerging biosensors and their promise for point-of-care applications", Chem. Soc. Rev., vol. 46, no. 2, pp. 366-388, 2017. CrossRef H. J. Chang et al., "Chiral Nonlinear Optics in Oxides, Polymers and Liquid Crystals", J. Korean Phys. Soc., vol. 43, no. 4, p. 587, 2003. DirectLink R. Bersohn, Y. Pao, and H. L. Frisch, "Double‐Quantum Light Scattering by Molecules", J. Chem. Phys., vol. 45, no. 9, pp. 3184-3198, Nov. 1966. CrossRef K. Clays and A. Persoons, "Hyper-Rayleigh scattering in solution", Phys. Rev. Lett., vol. 66, no. 23, pp. 2980-2983, 1991. CrossRef J. Campo, F. Desmet, W. Wenseleers, and E. Goovaerts, "Highly sensitive setup for tunable wavelength hyper-Rayleigh scattering with parallel detection and calibration data for various solvents", Opt. Express, vol. 17, no. 6, p. 4587, Mar. 2009. CrossRef S. R. Prabhu, A. Jayarama, K. Chandrasekharan, V. Upadhyaya, and S. W. Ng, "Synthesis, growth, structural characterization, Hirshfeld analysis and nonlinear optical studies of a methyl substituted chalcone", J. Mol. Struct., vol. 1136, pp. 244-252, May 2017. CrossRef K. Clays and A. Persoons, "Hyper‐Rayleigh scattering in solution", Rev. Sci. Instrum., vol. 63, no. 6, pp. 3285-3289, Jun. 1992. CrossRef K. Clays et al., "Nonlinear Optical Properties of Proteins Measured by Hyper-Rayleigh Scattering in Solution", Science (80-. )., vol. 262, no. 5138, pp. 1419-1422, Nov. 1993. CrossRef M. Frisch et al., Gaussian, Inc., Wallingford CT, 2009. DirectLink J. M. F. Custodio et al., "Chalcone as Potential Nonlinear Optical Material: A Combined Theoretical, Structural, and Spectroscopic Study", J. Phys. Chem. C, vol. 123, no. 10, pp. 5931-5941, Mar. 2019. CrossRef

Low-energy bands, optical properties, and spin/valley-Hall conductivity of silicene and germanene

2020 ◽  
Vol 55 (30) ◽  
pp. 14848-14857
Author(s):  
Pham Thi Huong ◽  
Do Muoi ◽  
Huynh V. Phuc ◽  
Chuong V. Nguyen ◽  
Le T. Hoa ◽  
...  
Keyword(s):  
Optical Properties ◽  
Low Energy ◽  
Hall Conductivity ◽  
Energy Bands

Low-energy bands and optical properties of monolayer WS2

Optik ◽  
2020 ◽  
Vol 209 ◽  
pp. 164581 ◽  
Author(s):  
Do Muoi ◽  
Nguyen N. Hieu ◽  
Van Thinh Pham ◽  
Huynh V. Phuc ◽  
Chuong V. Nguyen ◽  
...  
Keyword(s):  
Optical Properties ◽  
Low Energy ◽  
Energy Bands

NONLINEAR OPTICAL PROPERTIES OF mSTRAWBERRY AND mCHERRY FOR SECOND HARMONIC IMAGING

2010 ◽  
Vol 19 (01) ◽  
pp. 1-13 ◽  
Author(s):  
EVELIEN DE MEULENAERE ◽  
MARC DE WERGIFOSSE ◽  
EDITH BOTEK ◽  
STIJN SPAEPEN ◽  
BENOÎT CHAMPAGNE ◽  
...  
Keyword(s):  
Optical Properties ◽  
Nonlinear Optical ◽  
Rayleigh Scattering ◽  
Fluorescent Protein ◽  
Fluorescent Proteins ◽  
Second Harmonic ◽  
Harmonic Signal ◽  
Harmonic Imaging ◽  
Nonlinear Optical Properties ◽  
Lower Energy Band

The second-order nonlinear optical properties of two monomeric red fluorescent proteins, mStrawberry and mCherry, have been experimentally determined by frequency-resolved femtosecond hyper-Rayleigh scattering. These proteins were found to exhibit a stronger nonlinear response than the previously described eGFP, eYFP and DsRed,1 confirming the trend that fluorophores with a more extended conjugated system, or a lower-energy band gap between ground and excited state, exhibit a larger static hyperpolarizability (β0). Furthermore, these experimental data were complemented with quantum chemical calculations. A discrepancy was observed between experimental and theoretical results, but this could be explained by the chromophore model extracted from the available X-ray diffraction data. While eGFP showed a larger dynamic experimental response (βHRS) due to the highest resonance enhancement, we measured an even higher signal for mCherry. Furthermore, mCherry also shows a better separation of the second harmonic signal and two-photon excited fluorescent signal, making this the preferred fluorescent protein for second harmonic imaging at 800 nm so far.

SECOND-ORDER NONLINEAR OPTICAL PROPERTIES OF CHROMOPHORE-COATED PARTICLES: SYMMETRY CONSIDERATIONS

2007 ◽  
Vol 16 (01) ◽  
pp. 27-35 ◽  
Author(s):  
KASPER BAERT ◽  
KURT WOSTYN ◽  
RENAUD A. L. VALLÉE ◽  
KOEN CLAYS
Keyword(s):  
Optical Properties ◽  
Nonlinear Optical ◽  
Rayleigh Scattering ◽  
Second Harmonic ◽  
Nonlinear Effects ◽  
Second Order ◽  
Nonlinear Optical Properties ◽  
Harmonic Intensity ◽  
Nonlinear Optical Chromophores ◽  
Optical Chromophores

The second-order nonlinear optical properties of polystyrene particles coated with two well-characterized nonlinear optical chromophores with different molecular symmetry have been studied. From the markedly different depolarization ratio for the hyper-Rayleigh scattering from the molecular scatterers and from the largely different second-harmonic intensity from particles coated with these chromophores, we conjecture that contributions from antisymmetric molecular electronic states are necessary to observe second-order nonlinear effects from centrosymmetrical particles in isotropic solution.

scholarly journals Arylthienyl-vinyl-benzothiazoles as Efficient Second Harmonic Generators (SHG) for Nonlinear Optics

Proceedings ◽  
2018 ◽  
Vol 9 (1) ◽  
pp. 4 ◽  
Author(s):  
Rosa M. F. Batista ◽  
Susana P. G. Costa ◽  
Michael Belsley ◽  
M. Manuela M. Raposo
Keyword(s):  
Optical Properties ◽  
Nonlinear Optics ◽  
Nonlinear Optical ◽  
Rayleigh Scattering ◽  
Second Harmonic ◽  
Decomposition Temperature ◽  
Nonlinear Optical Properties ◽  
Nonlinear Properties ◽  
Harmonic Generator ◽  
Linear And Nonlinear

New push-pull second harmonic generation (SHG) chromophores 2 were synthesized in order to study their linear and nonlinear optical properties. The donor-acceptor π-conjugated systems 2 were prepared in good to excellent yields by a simple aldol-type condensation of the precursor aldehydes 1 with 6-nitro-2-methyl-1,3-benzothiazole in the presence of NaOH. Hyper-Rayleigh scattering in dioxane solutions was used to evaluate their second-order nonlinear optical properties. The experimental results showed that the optical (linear and nonlinear) properties are influenced by the electron-donor strength of the groups of the π-conjugated bridge. The vinyl-benzothiazole derivative 2b, with methoxyl as the donor group, exhibited the largest first hyperpolarizability β (1660 × 10−30 esu, 40 times greater than the standard reference pNA molecule) and the highest decomposition temperature (Td = 360 °C). The good balance between nonlinearity and thermal stability makes this compound a promising candidate as second harmonic generator (SHG) for nonlinear optics.

Theoretical Framework of 1,3-Thiazolium-5-Thiolates Mesoionic Compounds: Exploring the Nature of Photophysical Properties and Molecular Nonlinearity

2020 ◽  
Author(s):  
Zeyu Liu ◽  
Shugui Hua ◽  
Tian Lu ◽  
Ziqi Tian
Keyword(s):  
Optical Properties ◽  
Rational Design ◽  
Rayleigh Scattering ◽  
Function Analysis ◽  
Theoretical Calculations ◽  
Photophysical Properties ◽  
Optical Nonlinearity ◽  
Nonlinear Properties ◽  
Photoelectric Performance ◽  
Wave Function Analysis

Inspired by a previous experimental study on the first-order hyperpolarizabilities of 1,3-thiazolium-5-thiolates mesoionic compounds using Hyper-Rayleigh scattering technique, we theoretically investigated the UV-Vis absorption spectra and every order polarizabilities of these mesoionic molecules. Based on the fact that the photophysical and nonlinear properties observed in the experiment can be perfectly replicated, our theoretical calculations explored the essential characteristics of the optical properties of the mesoionic compounds with different electron-donating groups at the level of electronic structures through various wave function analysis methods. The influence of the electron-donating ability of the donor on the optical properties of the molecules and the contribution of the mesoionic ring moiety to their optical nonlinearity are clarified, which have not been reported by any research so far. This work will help people understand the nature of optical properties of mesoionic-based molecules and provide guidance for the rational design of molecules with excellent photoelectric performance in the future.

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