Benzo[<i>c</i>]thiophene Chromophores Linked to Cationic Fe and Ru Derivatives for NLO Materials: Synthesis Characterization and Quadratic Hyperpolarizabilities

Silva, Tiago J. L.; Mendes, Paulo J.; Garcia, M. Helena; Robalo, M. Paula; Ramalho, J. P. Prates; Carvalho, A.J. Palace; Büchert, Marina; Wittenburg, Christian; Heck, Jürgen

doi:10.1002/ejic.201300048

Cited by 9 publications

(5 citation statements)

References 64 publications

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“…Here, we report a series of octopolar D 2 -symmetric chromophores, based on the MPZnM motif, that demonstrate that strong electronic coupling between multiple charge-transfer oscillators can provide octopolar NLO chromophores that exhibit impressive β values at 1500 nm. While wavelengths near 1500 nm define a critically important telecommunications spectral region, no molecular chromophore has thus far been delineated that exhibits a dynamic hyperpolarizability measured at a 1.5 μm incident irradiation wavelength that exceeds 700 × 10 –30 esu; ,,,− this work provides new insights into the design of octopolar NLO chromophores, and demonstrates the utility of MPZnM compositions for realizing substantial β HRS values at long wavelengths.…”

Section: Introductionmentioning

confidence: 82%

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores

et al. 2016

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Octopolar D2-symmetric chromophores, based on the MPZnM supermolecular motif in which (porphinato)zinc(II) (PZn) and ruthenium(II) polypyridyl (M) structural units are connected via ethyne linkages, were synthesized. These structures take advantage of electron-rich meso-arylporphyrin or electron-poor meso-(perfluoroalkyl)porphyrin macrocycles, unsubstituted terpyridyl and 4′-pyrrolidinyl-2,2′;6′,2″-terpyridyl ligands, and modulation of metal(II) polypyridyl-to-(porphinato)zinc connectivity, to probe how electronic and geometric factors impact the measured hyperpolarizability. Transient absorption spectra obtained at early time delays (tdelay < 400 fs) demonstrate fast excited-state relaxation, and formation of a highly polarized T1 excited state; the T1 states of these chromophores display expansive, intense T1 → Tn absorption manifolds that dominate the 800–1200 nm region of the NIR, long (μs) triplet-state lifetimes, and unusually large NIR excited absorptive extinction coefficients [ε(T1 → Tn) ∼ 105 M–1 cm–1]. Dynamic hyperpolarizability (βλ) values were determined from hyper-Rayleigh light scattering (HRS) measurements, carried out at multiple incident irradiation wavelengths spanning the 800–1500 nm spectral domain. The measured βHRS value (4600 ± 1200 × 10–30 esu) for one of these complexes, RuPZnRu, is the largest yet reported for any chromophore at a 1500 nm irradiation wavelength, highlighting that appropriate engineering of strong electronic coupling between multiple charge-transfer oscillators provides a critical design strategy to realize octopolar NLO chromophores exhibiting large βHRS values at telecom-relevant wavelengths. Generalized Thomas–Kuhn sum (TKS) rules were utilized to compute the effective excited-state-to-excited-state transition dipole moments from experimental linear-absorption spectra; these data were then utilized to compute hyperpolarizabilities as a function of frequency, that include two- and three-state contributions for both βzzz and βxzx tensor components to the RuPZnRu hyperpolarizability spectrum. This analysis predicts that the βzzz and βxzx tensor contributions to the RuPZnRu hyperpolarizability spectrum maximize near 1550 nm, in agreement with experimental data. The TKS analysis suggests that relative to analogous dipolar chromophores, octopolar supermolecules will be likely characterized by more intricate dependences of the measured hyperpolarizability upon irradiation wavelength due to the interactions among multiple different β tensor components.

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Section: Introductionmentioning

confidence: 82%

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores

et al. 2016

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“…22,23 Recently, a series of novel 2-benzothiazole-, 4-pyridine-, and 2-and 4-quinoline-based styryl dyes containing an Nmethylbenzoaza-15(18)-crown-5(6)-ether moiety were synthesized, which have high performance as optical molecular sensors for alkali and alkaline-earth metal cations. 24 On the other hand, previous studies have demonstrated that cation recognition can be performed by probing the variation of the nonlinear optical (NLO) properties [25][26][27][28][29][30][31] such as the theoretical investigation on NLO molecular switches of spiropyran/merocyanine systems as selective cation sensors for alkali, alkaline earth, and transition metals. Different cations produce contrasting b 0 values because of the rst hyperpolarizability (b 0 ), depending strongly on the nature of the binding metal cations, which is the key for detecting cations.…”

Section: Introductionmentioning

confidence: 99%

N-Methylbenzoaza-18-crown-6-ether derivatives as efficient alkali metal cations sensors: the dipole moment and first hyperpolarizability

Gao

Sun

et al. 2014

RSC Adv.

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“…After showcasing the SPDAC as a potential tool for orthogonal cycloadditions with cyclooctynes, we next explored the reactivity of these sulphur‐based mesoionics with arynes . The importance of benzo[c]thiophenes in materials science, in particular for their nonlinear optical (NLO) properties, low band gap conjugated polymers, and their use as near‐infrared fluorophore subunits is well‐established . Nonetheless, synthetic access to benzo[c]thiophenes and derived S‐heteroacenes still remains challenging and requires time‐consuming, multistep convergent approaches.…”

Section: Methodsmentioning

confidence: 99%

Strain‐Promoted 1,3‐Dithiolium‐4‐olates–Alkyne Cycloaddition

et al. 2019

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Reported here is the reactivity of mesoionic 1,3‐dithiolium‐4‐olates towards strained alkynes, leading to thiophene cycloaddition products. In the process, the potential of these dipoles towards orthogonal reaction with azides, allowing efficient double ligation reactions, was discovered. A versatile process to access benzo[c]thiophenes, in an unprecedented divergent fashion, was developed and provides a new entry to unconventional polyaromatic thiophenes.

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Benzo[c]thiophene Chromophores Linked to Cationic Fe and Ru Derivatives for NLO Materials: Synthesis Characterization and Quadratic Hyperpolarizabilities

Cited by 9 publications

References 64 publications

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores

N-Methylbenzoaza-18-crown-6-ether derivatives as efficient alkali metal cations sensors: the dipole moment and first hyperpolarizability

Strain‐Promoted 1,3‐Dithiolium‐4‐olates–Alkyne Cycloaddition

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