Group 8 metal alkynyl complexes for nonlinear optics

Grelaud, Guillaume; Cifuentes, Marie P.; Paul, Frédéric; Humphrey, Mark G.

doi:10.1016/j.jorganchem.2013.10.008

Cited by 78 publications

(72 citation statements)

References 88 publications

(112 reference statements)

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“…Both the spatial elongation of the π ‐manifold of each branch and their polarization ( via the terminal X substituents) will induce an increase of the 2PA cross‐sections. In this respect, it has independently been established that the inclusion of electron‐rich d 6 transition metal centers via alkynyl linkages constitutes an efficient alternative strategy for boosting the second‐ and third‐order NLO properties of such carbon‐rich structures . For instance, cross‐sections above 400 GM were found for the known isocyanurate derivatives 21 and 22 (Scheme ) .…”

Section: Resultsmentioning

confidence: 99%

Triarylisocyanurate‐Based Fluorescent Two‐Photon Absorbers

et al. 2020

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The synthesis and characterization of six triarylisocyanurates, featuring 2,7‐fluorenyl or 9,10‐anthracenyl groups incorporated in their peripheral arms are reported. Photophysical studies reveal that these new octupolar derivatives are more fluorescent (ΦF≥0.60 for all new compounds except for 1,3,5‐tri(9H‐fluoren‐2‐yl)‐1,3,5‐triazinane‐2,4,6‐trione 3) and present a red‐shifted lowest absorption and emission compared to their known phenyl analogues of comparable size. Depending on the nature of the terminal substituent, fast intramolecular energy transfer among the three arms or localization of the excitation on a single branch occurs after population of their first singlet excited state. The latter effect was only observed in the presence of strongly electron‐releasing substituents in polar media. These new chromophores are also better two‐photon absorbers than the 1,4‐phenylene‐based isocyanurates reported so far, with cross sections σ2≥500 GM at 770 nm for 4‐NPh2 the fluorenyl group containing (13) and the anthracenyl group containing (14) chromophores. All these spectroscopic features, analyzed with the help of quantum chemical calculations, are crucial for the design of new biphotonic fluorescent dyes.

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Section: Resultsmentioning

confidence: 99%

Triarylisocyanurate‐Based Fluorescent Two‐Photon Absorbers

et al. 2020

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“…As for the absorption coefficients, Ru–vinylhelicenes 2 a , b show experimental IR spectra that are much more intense than their corresponding organic helicenes (4 times for mono and 10 times for bis‐Ru derivatives), owing to stronger electric dipole transition moments. This effect is often encountered in organometallic species that introduce more charge density in the structure 19. Electronic low‐lying levels introduced by some metallic ions can also induce VCD enhancement 20.…”

Section: Resultsmentioning

confidence: 99%

Ruthenium‐Grafted Vinylhelicenes: Chiroptical Properties and Redox Switching

Srebro

Anger

Moore

et al. 2015

Chemistry A European J

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The properties of mono- and bis-Ru-vinyl[6]helicene complexes (2 a and 2 b, respectively), recently synthesized by using molecular engineering of helicenes based on the grafting of lateral organometallic substituents on the π-helical backbone through a vinyl bridge, are presented. These helicene derivatives are thoroughly characterized, with special attention given to their chiroptical properties and redox switching activity. The UV/Vis and electronic circular dichroism (ECD) spectra of P and M enantiopure species, both in the neutral and oxidized states ([2 a](·+), [2 b](·+), and [2 b](2+)), are analyzed with the aid of quantum-chemical calculations. The extended π-conjugation facilitated by the vinyl moiety, clearly visible in the electronic structures of 2 a,b, introduces new active bands in the ECD spectra that consequently lead to a significant increase in optical rotation of Ru-vinylhelicenes compared with the organic precursors. The vibrational circular dichroism (VCD) spectra were measured and calculated for both the organic and organometallic species and constitute the first examples of VCD for metal-based helicene derivatives. Finally, the redox-triggered chiroptical switching activity of 2 a,b is examined in detail by using ECD spectroscopy. The modifications of the ECD spectra in the UV/Vis and NIR region are well reproduced and rationalized by calculations.

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Section: ■ Introductionmentioning

confidence: 99%

“…4,20 Among different organometallic architectures, metal− acetylide-containing small molecules and polymers are of interest due to strong interactions between the metal d-orbitals and the π-system of the ligand mediated via the metal− acetylide linkage. 21 In the present investigation, we explored the properties of ET-BTD-TE (E = ethynylene, T = 3-hexyl-2,5-thienylene, BTD = 2,1,3-benzothiadiazole) containing organometallic complexes for optoelectronic properties as well as 2PA, where BTD acts as an acceptor and T acts as a donor (Chart 1).…”

Section: ■ Introductionmentioning

confidence: 99%

Photophysics and Nonlinear Absorption of Gold(I) and Platinum(II) Donor–Acceptor–Donor Chromophores

2015

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A series of Au(I) and Pt(II) acetylide complexes of a π-conjugated donor-acceptor-donor (D-A-D) chromophore were studied to develop quantitative structure-property relationships for their photophysical and nonlinear optical properties. The D-A-D chromophore consists of a "TBT" unit, where T = 3-hexyl-2,5-thienylene and BTD = 2,1,3-benzothiadiazole, capped with ethynylene groups. The D-A-D chromophore is functionalized with Au(I)PR3 (R = -Me and -Ph) and trans-Pt(II)(PR3)2-CCPh (R = -Me and -Bu) "auxochromes". All of the metal complexes were characterized by ground-state absorption, photoluminescence, nanosecond transient absorption, and two-photon absorption (2PA) spectroscopy. The experiments provided quantitative values of the photophysical parameters, including rates for radiative decay and intersystem crossing (ISC), triplet yields, and two-photon absorption cross sections. Pronounced solvatochromism in the fluorescence spectra suggests an enhanced dipole moment in the excited state of the complexes compared to the unmetalated TBT chromophore. The gold complexes feature larger fluorescence quantum yields and longer emission lifetimes compared to platinum. The Pt(II) complexes exhibit enhanced triplet-triplet absorption, reduced triplet-state lifetimes, and larger singlet oxygen quantum yields, consistent with more efficient ISC compared to the Au(I) complexes. When excited by 100 fs pulses, all of the D-A-D chromophores exhibit moderate two-photon absorption in the near-infrared between 700 and 900 nm. The 2PA cross section for the Au(I) complexes is almost the same as the unmetalated D-A-D chromophore (∼100 GM). The Pt(II) complexes exhibit significantly enhanced 2PA compared to the other chromophores, reaching 1000 GM at 750 nm. Taken together, the results indicate that the Pt(II) center is considerably more effective in inducing singlet-triplet ISC and in enhancing the 2PA cross section. This result reveals the greater promise for Pt(II) acetylides in chromophores for temporal and frequency agile nonlinear absorption.

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Group 8 metal alkynyl complexes for nonlinear optics

Cited by 78 publications

References 88 publications

Triarylisocyanurate‐Based Fluorescent Two‐Photon Absorbers

Triarylisocyanurate‐Based Fluorescent Two‐Photon Absorbers

Ruthenium‐Grafted Vinylhelicenes: Chiroptical Properties and Redox Switching

Photophysics and Nonlinear Absorption of Gold(I) and Platinum(II) Donor–Acceptor–Donor Chromophores

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