Exceptionally large two- and three-photon absorption cross-sections by OPV organometalation

Gao, Beibei; Mazur, Leszek Mateusz; Morshedi, Mahbod; Barlow, Adam; Wang, Huan; Quintana, Cristóbal; Zhang, Chi; Samoć, Marek; Cifuentes, Marie P.; Humphrey, Mark G.

doi:10.1039/c6cc02560a

Cited by 26 publications

(13 citation statements)

References 32 publications

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“…The Z‐scan technique has therefore been used, but the required spectral‐dependence studies are time consuming, and metal–alkynyl examples are limited (see, for example, Refs. , , , , , , ).…”

Section: Introductionmentioning

confidence: 90%

Linear Optical, Quadratic and Cubic Nonlinear Optical, Electrochemical, and Theoretical Studies of “Rigid‐Rod” Bis‐Alkynyl Ruthenium Complexes

et al. 2018

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The syntheses of oligo(p‐phenylene ethynylene)s (OPEs) end‐functionalized by a nitro acceptor group and with a ligated ruthenium unit at varying locations in the OPE chain, namely, trans‐[Ru{(C≡C‐1,4‐C6H4)nNO2}(C≡CR)(dppe)2] (dppe=1,2‐bis(diphenylphosphino)ethane; n=1, R=1,4‐C6H4C≡C‐1,4‐C6H4C≡CPh, 1,4‐C6H4NEt2; n=2, R=Ph, 1,4‐C6H4C≡CPh, 1,4‐C6H4C≡C‐1,4‐C6H4C≡CPh, 1,4‐C6H4NO2, 1,4‐C6H4NEt2; n=3, R=Ph, 1,4‐C6H4C≡CPh), are reported. Their electrochemical properties were assessed by cyclic voltammetry, their linear optical properties and quadratic and cubic nonlinear optical properties were assayed by UV/Vis/NIR spectroscopy, hyper‐Rayleigh scattering studies employing nanosecond pulses at 1064 nm, and broad spectral range Z‐scan studies employing femtosecond pulses, respectively, and their linear optical properties and vibrational spectroscopic behavior in the formally RuIII state was examined by UV/Vis/NIR and IR spectroelectrochemistry, respectively. The potentials of the metal‐localized oxidation processes are sensitive to alkynyl‐ligand modification, but this effect is attenuated on π‐bridge lengthening. Computational studies employing time‐dependent density functional theory were undertaken on model complexes, with a 2D scan revealing a soft potential‐energy surface for intra‐alkynyl‐ligand aryl‐ring rotation; this is consistent with the experimentally observed blueshift in optical absorption maxima. Quadratic optical nonlinearities are significant and cubic NLO coefficients for these small complexes are small. The optimum length of the alkynyl ligands and the ideal metal location in the OPE to maximize the key coefficients have been defined.

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Section: Introductionmentioning

confidence: 90%

Linear Optical, Quadratic and Cubic Nonlinear Optical, Electrochemical, and Theoretical Studies of “Rigid‐Rod” Bis‐Alkynyl Ruthenium Complexes

et al. 2018

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“…In particular, coordination and organometallic complexes have attracted significant attention because they expand the possibilities for tuning NLO properties by varying the metal center (and its oxidation state and co‐ligands) when compared to organic chromophores . Metallocenyl and metal alkynyl complexes are the two most scrutinized classes of NLO‐active organometallic complexes, with the latter being found to exhibit record values of nonlinear optical coefficients …”

Section: Introductionmentioning

confidence: 99%

Long‐Range Corrected DFT Calculations of First Hyperpolarizabilities and Excitation Energies of Metal Alkynyl Complexes

2018

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The performance of the CAM-B3LYP, ωB97X and LC-BLYP long-range corrected density functional theory methods in the calculation of molecular first hyperpolarizabilities (β) and low-lying charge transfer (CT) excitation energies of the metal alkynyl complexes M(C≡C-4-C H -1-NO )(κ -dppe)(η -C H ) [M=Fe (1), Ru (2), Os (3)] and trans-[Ru{C≡C-(1,4-C H C≡C) -4-C H -1-NO }Cl(κ -dppm) ] [n=0 (4), 1 (5), 2 (6)] was assessed. The BLYP, B3LYP and PBE0 standard exchange-correlation functionals and the Hartree-Fock method were also examined. The BLYP functional was shown to perform poorly in the calculation of β and low-energy CT transitions. The hybrid functionals (B3LYP and PBE0) showed significant improvement over the pure functional BLYP, but overestimated the hyperpolarizability ratios and the wavelengths of the lowest energy metal-to-ligand CT transitions for 5 and 6. The effect of long-range corrections is noteworthy, particularly for the larger complexes, improving the calculation of β ratios for 4-6. However, CAM-B3LYP, ωB97X, and LC-BLYP considerably overestimated the low-lying CT energies. PBE0 was found to give the best transition energy match for 4. The influence of the phenylene ring orientation in the alkynyl ligand on the calculated properties is substantial, particularly for the larger complexes. For these types of calculations, a basis set with diffuse functions (at least 6-31+G(d)) for the heavy elements is recommended.

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“…Nevertheless, the current observation is in agreement with previously reported studies based on different molecular systems, in which the structural expansion was also found to correlate with 2PA and 3PA cross-sections. 16,17 It is also noted that the maximal 2PA and 3PA of these two dye molecules are located at wavelengths shorter than twice and three-times their lowest-energy linear absorption maxima (i.e. l 2PA max < 2l 1PA max and l 3PA max < 3l 1PA max for both studied compounds).…”

Section: Optical Propertiesmentioning

confidence: 79%

Multi-photon properties of branched chromophores derived from indenoquinoxaline and oxadiazole heterocyclic units

et al. 2021

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Exceptionally large two- and three-photon absorption cross-sections by OPV organometalation

Cited by 26 publications

References 32 publications

Linear Optical, Quadratic and Cubic Nonlinear Optical, Electrochemical, and Theoretical Studies of “Rigid‐Rod” Bis‐Alkynyl Ruthenium Complexes

Linear Optical, Quadratic and Cubic Nonlinear Optical, Electrochemical, and Theoretical Studies of “Rigid‐Rod” Bis‐Alkynyl Ruthenium Complexes

Long‐Range Corrected DFT Calculations of First Hyperpolarizabilities and Excitation Energies of Metal Alkynyl Complexes

Multi-photon properties of branched chromophores derived from indenoquinoxaline and oxadiazole heterocyclic units

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