Modified<i>p</i>-phenylene vinylene platinum (II) acetylides with enhanced two-photon absorption in solid host

Dubinina, Galyna G.; Price, Randi S.; Wicks, Geoffrey; Wnuk, Paweł; Stepanenko, Yuriy; Drobizhev, Mikhail; Rebane, Aleksander; Schanze, Kirk S.

doi:10.1117/12.2004180

Cited by 3 publications

(5 citation statements)

References 21 publications

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“…The relative amplitude of electronic coupling between the anchoring groups attached to the ethynyl functions are well-known from electrochemical investigations, using redox-active ferrocenyl probes, and from photophysical measurements . The redox and optically active [Pt] -containing polymers share a common structure, ( [Pt] - G ) n , where G is most of the time an organic fragment, which found applications in 2-photon absorption, solar cells, and light emitting diodes . However, the cases where G is either composed of organometallic residues or coordination moieties are far more scarce.…”

Section: Introductionmentioning

confidence: 99%

Luminescent 1D- and 2D-Coordination Polymers Using CuX Salts (X = Cl, Br, I) and a Metal-Containing Dithioether Ligand

et al. 2016

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The organometallic synthon trans-[p-MeSCHC≡C-Pt(PMe)-C≡CCHSMe] (L1) reacts with CuX (X = Cl, Br, I) in PrCN and PhCN to form 1D- or 2D-coordination polymers (CP) with a very high degree of variability of features. The copper-halide unit can be either the rhomboids CuX fragments or the step cubane CuI. The CP's may also incorporate a crystallization solvent molecule or not, which may be coordinated to copper or not. Their characterizations were performed by X-ray crystallography, thermal gravimetric analysis (TGA), and IR, absorption, and emission spectra as well as photophysical measurements in the presence and absence of solvent crystallization molecules. The nature of the singlet and triplet excited state was addressed using DFT and TDDFT computations, which turn out to be mainly ππ* with some minor MLCT (CuI → L1) contributions. The porosity of the materials has been evaluated by BET (N at 77 K). The solvent-free 1D CP's are not prone to capture solvent molecules or CO, but the efficiency for CO absorption is best for the 2D CP, which exhibits the presence of clear cavities in the grid structure, after the removal of the crystallization molecules.

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Section: Introductionmentioning

confidence: 99%

Luminescent 1D- and 2D-Coordination Polymers Using CuX Salts (X = Cl, Br, I) and a Metal-Containing Dithioether Ligand

et al. 2016

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“… d Lifetime is less than the instrument time resolution which is ∼100 ps. e Previously published data f Previously published data …”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of the linear and cross-conjugated complexes in Scheme have been reported previously. , PMMA monoliths were prepared by a procedure adapted from Westlund and co-workers . The platinum(II) acetylide chromophores (initial concentration 1 mM) and 6 mg of azoisobutyronitrile (AIBN) were dissolved in 1.1 mL of inhibitor-free methyl methacrylate (MMA).…”

Section: Methodsmentioning

confidence: 99%

“…25 The series of p-phenylenevinylene platinum(II) acetylide complexes in Figure 2 were recently shown to exhibit extraordinarily large two-photon absorption (2PA) crosssection values (up to 10 000 GM). 26,27 In this work, we explored two series of chromophores to elucidate their structure−property relationships for optical power limiting. In particular, the "linear" series TPVn has two oligo p-phenyl-enevinylene (OPV) chromophores linked to a platinum center through a triphenylamine group with an increasing number OPV units (n = 0−2, where n is the number of phenylenes between the terminal triphenylamine groups).…”

Section: ■ Introductionmentioning

confidence: 99%

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Polymer Monoliths Containing Two-Photon Absorbing Phenylenevinylene Platinum(II) Acetylide Chromophores for Optical Power Limiting

Price

Dubinina

Wicks

et al. 2015

ACS Appl. Mater. Interfaces

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A series of platinum(II) acetylide complexes containing p-phenylenevinylene and moieties end-capped with triphenylamine groups have been incorporated into poly(methyl methacrylate) (PMMA) monoliths for optical power limiting applications. The one- and two-photon photophysical properties were investigated and compared to the photophysical properties in THF. The absolute two-photon absorption cross-section values for the monolith samples were measured and are comparable to the values obtained in solution. In the PMMA monoliths, the complexes retained the important two-photon absorption and reverse saturable absorption properties necessary for optical power limiting via dual mode mechanism, and their strong nonlinear absorption property was demonstrated by the open-aperture Z-scan method. Photostability studies of the p-phenylenevinylene platinum(II) acetylide complexes showed two photodegradation processes: a trans-to-cis isomerization and a singlet-oxygen sensitized self-oxidative cleavage. The photostability of the least photostable complex TPV0 was increased upon incorporation into a PMMA matrix.

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“…Previous work has sought to incorporate Pt-acetylide nonlinear chromophores into glassy matrices including PMMA and sol–gel glasses. ,,,,− In the case of PMMA, methods of incorporating the chromophores include both covalent attachment and dispersion into the polymer matrix. However, these methods have resulted in solids with chromophore concentration ranging from 1 to 100 mM (chromophore concentration in the polymer matrix).…”

Section: Discussionmentioning

confidence: 99%

Polymeric Nonlinear Absorption Chromophore Array from Controlled Radical Polymerization and “Click” Chemistry

Chen

Liao

Price

et al. 2020

ACS Appl. Polym. Mater.

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A polyacrylate with pendant nonlinear absorption (NLA) chromophores was prepared via the reversible addition−fragmentation (RAFT)−click synthetic strategy. The polyacrylate backbone of the NLA polymer was constructed by reversible addition−fragmentation (RAFT) polymerization and subsequently modified to azide-containing "clickable polymers". Platinum acetylide chromophores that exhibit NLA via both two-photon absorption (TPA) and excited-state absorption (ESA) mechanisms were subsequently attached to the azide-substituted polyacrylate via copper(I)-catalyzed azide−alkyne cycloaddition. The resulting polymer exhibits similar photophysical properties to the platinum acetylide precursor chromophore, including steady-state absorption and emission, triplet−triplet transient absorption, and nonlinear absorption properties. In addition, the resulting polymers can be spin-coated to afford an optically transparent film, which also preserved the nonlinear absorption characteristics of the chromophores.

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Modifiedp-phenylene vinylene platinum (II) acetylides with enhanced two-photon absorption in solid host

Cited by 3 publications

References 21 publications

Luminescent 1D- and 2D-Coordination Polymers Using CuX Salts (X = Cl, Br, I) and a Metal-Containing Dithioether Ligand

Luminescent 1D- and 2D-Coordination Polymers Using CuX Salts (X = Cl, Br, I) and a Metal-Containing Dithioether Ligand

Polymer Monoliths Containing Two-Photon Absorbing Phenylenevinylene Platinum(II) Acetylide Chromophores for Optical Power Limiting

Polymeric Nonlinear Absorption Chromophore Array from Controlled Radical Polymerization and “Click” Chemistry

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