Long-lifetime reverse saturable absorption in a bipyridyl platinum(II) complex bearing naphthalimidylethynyl-substituted fluorenylacetylide ligands

Pritchett, Timothy M.; Ferry, Michael J.; Mott, Andrew G.; Shensky, William M.; Haley, Joy E.; Li, Rui; Sun, Wenfang

doi:10.1016/j.optmat.2014.11.025

Cited by 14 publications

(13 citation statements)

References 25 publications

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“…In order to facilitate RSA of nanosecond laser pulses, an absorber should have a weak ground‐state absorption to populate the excited states, but long–lived triplet excited states, large triplet‐triplet excited‐state absorption coefficients, and a high quantum yield for triplet excited‐state formation. In recent years, the RSA of heavy transition‐metal complexes, such as octahedral Ir(III) complexes, have been extensively explored by our group, , , , and other groups, because these complexes displayed the aforementioned characteristics that well match the requirements for RSA. In addition, by structural modifications, both the ground‐ and excited‐state properties can be readily tuned in these complexes for optimization of the RSA.…”

Section: Introductionmentioning

confidence: 99%

Monocationic Iridium(III) Complexes with Far‐Red Charge‐Transfer Absorption and Near‐IR Emission: Synthesis, Photophysics, and Reverse Saturable Absorption

et al. 2019

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The synthesis, photophysics, and reverse saturable absorption (RSA) of three monocationic iridium(III) complexes (Ir1–Ir3) bearing diimine (N^N) ligand with different degrees of π‐conjugation are reported. Spectroscopic methods, including UV/Vis absorption, emission, and transient absorption spectroscopy, and density functional theory calculations were carried out to understand the nature of the singlet and triplet optical transitions and the influence of N^N ligand π‐conjugation on the photophysical properties of the complexes. All complexes possessed predominant ligand–centered, 1π,π* absorption bands at 280–420 nm and weak charge‐transfer absorption bands at 420–610 nm for Ir1, 420–680 nm for Ir2, and 420–730 nm for Ir3. The extended π‐conjugation of the N^N ligand red–shifted the charge‐transfer absorption bands and increased the molar extinction coefficients of all of the absorption bands. All complexes were emissive in the far‐red to the near‐infrared regions, with the emission energies gradually decreasing when the π‐conjugation of the N^N ligand increased. However, the emission lifetime of Ir3 increased when its emitting state energy decreased. This was caused by the different nature of the T1 state in Ir3, which was the predominant N^N ligand–localized 3π,π* state compared to the charge‐transfer T1 states in Ir1 and Ir2. The different parentage of the T1 state in Ir3 also gave rise to a much broader and stronger triplet excited‐state absorption in the 420–800 nm regions. The varied ground‐state and triplet excited‐state absorption characteristics led to a different strength of the reverse saturable absorption (RSA) for ns laser pulses at 532 nm, with the RSA strength following the trend of Ir3 > Ir1 ≥ Ir2. Complex Ir3 is particularly attractive for its potential as a broadband reverse saturable absorber in view of its broader ground‐ and excited‐state absorption in the regions of 420–730 nm and longer–lived triplet excited state.

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Section: Introductionmentioning

confidence: 99%

Monocationic Iridium(III) Complexes with Far‐Red Charge‐Transfer Absorption and Near‐IR Emission: Synthesis, Photophysics, and Reverse Saturable Absorption

et al. 2019

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“…8,9 This is also confirmed by previous studies on their absorption in the excited states and the ground state to define population dynamics as well as lifetime and absorption cross-section parameters. [10][11][12] The NLO properties of phthalocyanines can be easily tuned by modifying their structures, mainly by the introduction of different substituents into the macrocycles, reducing the symmetry of the molecules. 13 However, uncontrolled aggregation of the macrocyclic molecules in highly concentrated solutions, as well as in nonhomogeneous films and spontaneously formed solid phases, worsens the expected characteristics in practice.…”

Section: Introductionmentioning

confidence: 99%

Thermally stable J-type phthalocyanine dimers as new non-linear absorbers for low-threshold optical limiters

Tolbin

Savelyev

Gerasimenko

et al. 2016

Phys. Chem. Chem. Phys.

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The possibility of developing new advanced optical limiters of laser radiation at 532 nm with low limiting thresholds has been demonstrated on thermally stable phthalocyanine J-type dimeric complexes of Mg, Zn, Cu, Ni, and Co. A new "threshold" model based on radiative transfer phenomena in nonlinear optical media was suggested for the exact definition of nonlinear absorption coefficient β and optical limiting threshold Ic. This model allows the determination of the optical characteristics of the limiter in the same active material with layers of different thicknesses, as well as the use of different parameters of laser radiation, such as cross-sectional spatial profiles of the laser beam and shapes of the laser pulse over time. The maximum value of the nonlinear absorption coefficient (β = 360 cm GW(-1)) and the lowest limiting threshold (Ic = 0.03 J cm(-2)) were estimated for a J-type zinc phthalocyanine dimer.

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“…Donor–bridge–acceptor molecular architectures are ideal platforms to study electron transfer. In particular, the square-planar coordination environment in platinum(II) complexes provides synthetic versatility and a well-defined directionality of electron transfer. − …”

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¹³C or Not ¹³C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides

et al. 2016

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Asymmetric isotopic labeling of parallel and identical electron- or energy-transfer pathways in symmetrical molecular assemblies is an extremely challenging task owing to the inherent lack of isotopic selectivity in conventional synthetic methods. Yet, it would be a highly valuable tool in the study and control of complex light-matter interactions in molecular systems by exclusively and nonintrusively labeling one of otherwise identical reaction pathways, potentially directing charge and energy transport along a chosen path. Here we describe the first selective synthetic route to asymmetrically labeled organometallic compounds, on the example of charge-transfer platinum(II) cis-acetylide complexes. We demonstrate the selective (13)C labeling of one of two acetylide groups. We further show that such isotopic labeling successfully decouples the two ν(C≡C) in the mid-IR region, permitting independent spectroscopic monitoring of two otherwise identical electron-transfer pathways, along the (12)C≡(12)C and (13)C≡(13)C coordinates. Quantum-mechanical mixing leads to intriguing complex features in the vibrational spectra of such species, which we successfully model by full-dimensional anharmonically corrected DFT calculations, despite the large size of these systems. The synthetic route developed and demonstrated herein should lead to a great diversity of asymmetric organometallic complexes inaccessible otherwise, opening up a plethora of opportunities to advance the fundamental understanding and control of light-matter interactions in molecular systems.

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Long-lifetime reverse saturable absorption in a bipyridyl platinum(II) complex bearing naphthalimidylethynyl-substituted fluorenylacetylide ligands

Cited by 14 publications

References 25 publications

Monocationic Iridium(III) Complexes with Far‐Red Charge‐Transfer Absorption and Near‐IR Emission: Synthesis, Photophysics, and Reverse Saturable Absorption

Monocationic Iridium(III) Complexes with Far‐Red Charge‐Transfer Absorption and Near‐IR Emission: Synthesis, Photophysics, and Reverse Saturable Absorption

Thermally stable J-type phthalocyanine dimers as new non-linear absorbers for low-threshold optical limiters

¹³C or Not ¹³C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides

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Long-lifetime reverse saturable absorption in a bipyridyl platinum(II) complex bearing naphthalimidylethynyl-substituted fluorenylacetylide ligands

Cited by 14 publications

References 25 publications

Monocationic Iridium(III) Complexes with Far‐Red Charge‐Transfer Absorption and Near‐IR Emission: Synthesis, Photophysics, and Reverse Saturable Absorption

Monocationic Iridium(III) Complexes with Far‐Red Charge‐Transfer Absorption and Near‐IR Emission: Synthesis, Photophysics, and Reverse Saturable Absorption

Thermally stable J-type phthalocyanine dimers as new non-linear absorbers for low-threshold optical limiters

13C or Not 13C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides

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¹³C or Not ¹³C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides