Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges

Zhang, Huihua; Morshedi, Mahbod; Kodikara, Mahesh S.; Moxey, Graeme J.; Wang, Genmiao; Wang, Huan; Quintana, Cristóbal; Stranger, Rob; Zhang, Chi; Cifuentes, Marie P.; Humphrey, Mark G.

doi:10.1002/cplu.201600203

Cited by 5 publications

(11 citation statements)

References 54 publications

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“…The quadratic nonlinearities of 1 – 18 were determined at 1064 nm using the hyper‐Rayleigh scattering (HRS) technique; the results are presented in Table , together with the two‐level corrected values. We have discussed shortcomings with the two‐level model in previous reports; although it is not generally considered adequate for donor–bridge–acceptor organometallic complexes such as those in the present study, it may have some utility in cases where the structural variation is restricted to the molecular components responsible for the low‐energy charge‐transfer bands in the linear optical spectrum . The hyperpolarizability data were confirmed to be free of multiphoton‐induced fluorescence.…”

Section: Resultssupporting

confidence: 80%

“…The intense low‐energy bands in the linear optical spectra of ruthenium mono‐alkynyl complexes of this type have been assigned previously as metal‐to‐ligand charge transfer (MLCT) in character . In the present study, we have explored the dependence of the wavelength of the optical absorption maxima on the nature of the alkynyl ligands.…”

Section: Resultsmentioning

confidence: 85%

“…Table summarizes results of cyclic voltammetric studies for ruthenium–alkynyl complexes 1 – 10 , together with data acquired simultaneously from the related complexes 14 – 18 ; data for 11 – 14 have been reported previously and those for 14 are in agreement with the present data . It is widely accepted that the HOMO in such ruthenium–alkynyl complexes has considerable contribution from the metal‐adjacent phenylalkynyl group, in addition to the expected metal character, but for conciseness we have labeled the first oxidation processes as Ru II/III ; we emphasize that this simplification should be borne in mind. The Ru II/III oxidation processes for the non‐functionalized chloro‐alkynyl complexes are typically reversible, occurring at potentials of approximately 0.55 V and invariant on π‐system lengthening by addition of further phenylene ethynylene units (proceeding from 14 to 15 and then to 1 ).…”

Section: Resultsmentioning

confidence: 99%

“…The electrochemical properties of ruthenium–alkynyl complexes have attracted considerable interest . Table summarizes results of cyclic voltammetric studies for ruthenium–alkynyl complexes 1 – 10 , together with data acquired simultaneously from the related complexes 14 – 18 ; data for 11 – 14 have been reported previously and those for 14 are in agreement with the present data .…”

Section: Resultsmentioning

confidence: 99%

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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: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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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 contrast, EFISH requires a knowledge of the third‐order polarizability γ and the dipole moment μ to extract β, and is inapplicable for ionic species and nonpolar molecules . For the past decade, HRS has been the method of choice in determining the quadratic hyperpolarizabilities of metal alkynyl complexes ,…”

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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Computational studies of the nonlinear optical properties of organometallic complexes

Kodikara

Stranger

Humphrey

2018

Coordination Chemistry Reviews

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Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges

Cited by 5 publications

References 54 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

Computational studies of the nonlinear optical properties of organometallic complexes

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