Investigation of the second hyperpolarizability of Ru-alkynyl complexes by z-scan and nonlinear scattering (original) (raw)
Related papers
Analytical Chemistry, 2017
Organic materials are promising candidates for integration in optical network components allowing fast communication. Ultimate speeds can be obtained by exploiting third-order nonlinear optical light-matter interactions that ultimately rely on the molecular second hyperpolarizability (γ). The exploration of molecular structure-property relations is crucial to optimize γ, but requires state of the art measurement techniques which are both sensitive and efficient. Unfortunately, present-day methods for probing the performance of third-order nonlinear optical (NLO) materials fail to meet at least one of those requirements. We have developed third-harmonic scattering (THS) as an alternative method to measure γ in solution, featuring a simple experimental setup and straightforward data analysis. Since the signal strength relies on |γ| 2 , the method proves to be very sensitive and allows rapid screening of organic molecules in dilute solutions for potential use in third-order NLO applications. In this manuscript, we demonstrate the experimental procedure and calibration of THS and have determined the second hyperpolarizability |γ| of commonly used solvents, which can be used as an internal calibration standard. As a proof of concept we determined γ of trans-stilbene, and found it to be in excellent agreement with values obtained by other techniques.
2008 2nd ICTON Mediterranean Winter, 2008
Theoretical calculations of the third order nonlinear optical coefficient as well as theoretical simulation of UV-VIS absorption spectra for a new alkynyl-ruthenium complexes bearing terminal hydrogenbonding receptors was presented. The proposed theoretical approach rely on geometry optimisation and corresponding quantum chemical calculations based on semi-empirical ZINDO /1 method within a framework of the restricted Hartree-Fock approach. The theoretically calculated absorption spectral positions are blue shifted in comparison to the experimental spectra for all compounds what is connected with the strong solvent effect. The theoretical calculation show that the second-order hyperpolarizabilities γ depends from the wavelength of incident electromagnetic radiation. A substitution of the different groups at the end of back side group causes the substantial changes of both absorption spectra as well as nonlinear optical coefficients. We show a dramatic enhancement of the molecular cubic hyperpolarizability in these systems for several wavelength of incident light beam. Comparison of theoretical results with the experimental data is presented.
Inorganica Chimica Acta - INORG CHIM ACTA, 2003
The compounds (E)-4-XCCC6H4CHCHPh [X=SiMe3 (1), H (2)], 1,3,5-{(E)-4-XC6H4CHCH}3C6H3 [X=I (3), CCSiMe3 (4), CCH (5)], [Au{(E)-4-CCC6H4CHCHPh}(L)] [L=PPh3 (6), PMe3 (7)], [Au(4-CCC6H4CCPh)(L)] [L=PPh3 (8), PMe3 (9)], 1,3,5-[(Ph3P)Au{(E)-4-CCC6H4CHCH}]3C6H3 (10), trans-[Ru{(E)-4-CCHC6H4CHCHPh}Cl(dppm)2]PF6 (11), trans-[Ru{(E)-4-CCC6H4CHCHPh}Cl(L2)2] [L2=dppm (12), dppe (13)], [1,3,5-(trans-[(dppm)2ClRu{(E)-4-CCHC6H4CHCH}])3C6H3](PF6)3 (14), 1,3,5-(trans-[(L2)2ClRu{(E)-4-CCC6H4CHCH}])3C6H3 [L2=dppm (15), dppe (16)] and 1,3,5-(trans-[(dppe)2(PhCC)Ru{(E)-4-CCC6H4CHCH}])3C6H3 (17) have been prepared (and the identity of 6 confirmed by a single-crystal X-ray diffraction study), and their electrochemical (Ru complexes) and nonlinear optical (NLO) properties assessed. The ruthenium complexes display reversible (12, 13, 15–17) or nonreversible (11, 14) processes attributable to Ru-centered oxidation, at potentials similar to those of previously-investigated monoruthenium...
Journal of the American Chemical Society, 1999
The molecular quadratic and cubic optical nonlinearities of a series of aryldiazovinylidene complexes [Ru(C CPhN NAr)(PPh 3) 2 (h-C 5 H 5)][X] [Ar=Ph (1), C 6 H 4 OMen (n=2 (2), (3), 4 (4)), C 6 H 4 NO 2-4 (5), 3,5-C 6 H 3 (NO 2) 2 (6); X = BF 4 (a), Cl (b), Br (c), I (d), 4-MeC 6 H 4 SO 3 (e), NO 3 (f); not all combinations] have been assessed using hyper-Rayleigh scattering and Z-scan techniques, respectively. The quadratic optical nonlinearities at 1064 nm are consistent with (i) introduction of polarizing substituents (NO 2 , OMe c.f. H); (ii) location of nitro substituent [the conjugated 4-NO 2 c.f. the non-conjugated 3,5-(NO 2) 2 ]; (iii) dipolar composition (the strong donor-electron deficient bridge-strong acceptor composition of 5 and 6 c.f. the strong donor-electron deficient bridge-poor donor composition of 1-4); and (iv) introduction of polyatomic anion (e, f c.f. ad) all making significant contributions to the observed quadratic NLO responses. Absolute values for quadratic nonlinearities are lower than those of related alkynyl complexes. Complex 5d was assessed across three solvents, with the i HRS data following the trend acetone \ dichloromethane\ thf, in contrast to the trend in absorption maxima in these solvents. The cubic optical nonlinearities were measured at 800 nm; real components of the nonlinearities are negative, and the imaginary components are significant, consistent with two-photon absorption contributing to the observed responses. The incorporation of nitro substituent in progressing from 1-4 to 5 results in a significant increase in both k real and k.
Study on the third-order nonlinear optical properties of four dmit complexes by Z-scan technique
Applied Physics A-materials Science & Processing, 2011
Four novel dmit complexes: [(C2H5)4N][Ni (dmit)2], [(C3H7)4N][Ni(dmit)2], [(C2H5)4N][Au(dmit)2] and [(C3H7)4N][Au(dmit)2], abbreviated as EtNi, PrNi, EtAu, and PrAu, were synthesized. The third-order nonlinear optical properties of them in acetonitrile solutions were investigated by using the Z-scan technique with 20 ps pulses width at 1064 nm. When the on-axis irradiance at focus I 0 was 5.025 GW/cm2, the nonlinear refraction coefficient n 2, the third-order nonlinear susceptibility χ (3), the molecular second-order hyperpolarizability γ of the four types of material were obtained with subject to Z-scan curves, and these indexes were with the magnitudes of 10−18 m2/W, 10−13 esu, and 10−31 esu, respectively. The nonlinear absorption coefficient β of Ni samples had the 10−12 m/W scale. The impact of different metals and cations on the third-order nonlinear optical properties of materials was analyzed. Through the derivation, the result suggests that these dmit complexes are promising candidates for applications to nonlinear optical devices manufacture in the near-infrared waveband.
2 ) dppe, X 2 ) C≡C, Y 2 ) (E)-CH)CH (12), C≡C (18); L 2 ) dppe, X 2 ) (E)-CH)CH, Y 2 ) C≡C , (E)-CH)CH (16); L 2 ) dppm, X 2 ) C≡C, Y 2 ) (E)-CH)CH (13); L 2 ) dppm, X 2 ) (E)-CH)CH, Y 2 ) C≡C (15), (E)-CH)CH (17)] are reported, the latter being donorbridge-acceptor complexes varying in bridge composition by replacement of yne with E-ene linkages, together with their cyclic voltammetric data, linear optical, and quadratic nonlinear optical response data. Ru II/III oxidation potentials increase on replacing yne linkage by E-ene linkage at the phenylene adjacent to the metal center, and on replacing dppe by dppm co-ligands. The low-energy optical absorption maxima occur in the region 20400-23300 cm -1 and are metal-to-ligand charge-transfer (MLCT) in origin; these bands undergo a blue-shift upon π-bridge lengthening by addition of phenyleneethynylene units, and on replacing E-ene linkages by yne linkages. Time-dependent density functional theory calculations on model complexes have suggested assignments for the low-energy bands. The optical spectra of selected oxidized species contain low-energy ligand-to-metal charge transfer (LMCT) bands centered in the region 9760-11800 cm -1 . Quadratic molecular nonlinearities from hyper-Rayleigh scattering (HRS) studies at 1064 nm reveal an increase in the two-level-corrected 0 value on π-bridge lengthening, a trend that is not seen with values because of the blue-shift in λ max for this structural modification. Replacing yne linkages by E-ene linkage at the phenylene adjacent to the metal center or dppm co-ligand by dppe results in an increase in and 0 values. In contrast, quadratic molecular nonlinearities by HRS at 1300 nm or electric field-induced secondharmonic generation (EFISH) studies at 1907 nm do not afford clear trends. Houbrechts, S.; Kauranen, M.; Clays, K.; Persoons, A.
Third order optical nonlinearity of a novel chalcone derivative through Z scan technique
Indian Journal of Pure and Applied Physics
A novel chalcone derivative 4-{(1E,3Z)-3-(4-bromo phenyl]-3-[2-(2,4-dinitrophenyl) hydrazinylidene] prop-1-en-1-yl} phenol [BPDP] has been synthesized and structurally characterized by NMR and FTIR studies. The third order non-linear optical properties of the BPDP have been studied using single beam Z scan technique with a nanosecond-pulsed Nd: YAG laser source at 532 nm. The coefficient of non linear refraction (Ȗ) of the compound is found to be negative as revealed by the signature of closed aperture data. The results obtained under open aperture configuration indicate that the material exhibits reverse saturation absorption. The magnitude of real part of third-order optical susceptibility (Ȥ (3)) and of molecular second order hyperpolarizability (γ h) are found to be-3.5×10 −20 m 2 V −2 and-5.9×10 −48 m 5 V −2 , respectively. The thermo gravimetric analysis shows that the material possesses a very good thermal stability up to 203°C.
A DFT STUDY ON THE SONLO PROPERTIES OF OLIGO-THIOPHENE ACETYLIDE Ru COMPLEXES
2009
The search on organometallic compounds for the development of novel nonlinear optical (NLO) materials with large second-order nonlinearities (SONLO) is currently the subject of significant interest in view of their potential application in the area of integrated optics [1]. Experimental and computational systematic studies were made on half-sandwich organometallic complexes presenting the typical push-pull feature in which the metal centre, bound to a highly polarizable conjugated backbone, acts as an electron-releasing or withdrawing group. The results revealed that 5-monocyclopentadienylruthenium moiety can be very efficient electron-donor group in complexes presenting thiophene-based ligands with a nitro group as an electron acceptor [2,3]. Nevertheless, the understanding of the relationship between the structure and experimental molecular NLO phenomena is not completely clear, namely the effect of the conjugation length of the chromophores. Theoretical studies using time-depende...
Third-Harmonic Generation in Mixed-Valent Ru−Pyrazine Chains: A Theoretical Study
The Journal of Physical Chemistry A, 1997
We present and discuss the results of a numerical investigation on the susceptivity for third-harmonic generation in mixed valent ruthenium-pyrazine chains (which we may call "Creutz-Taube chains"), whose skeleton is made by ruthenium ions bridged by pyrazine ligands. These compounds are described by a two-band Hubbard Hamiltonian, which, according to our previous results, is capable of reproducing the main features of the optical spectra in the near-IR-vis as a function of the total charge of the ion (i.e., the number of Ru 2+ and Ru 3+ ions). The third-harmonic susceptivity, computed exactly through a linear algebraic method (avoiding the sum over states) is remarkably high, suggesting that these compounds may be good candidates for nonlinear optics and photonics.