Reversible Photoactivated Phosphorescence of Gold(I) Arylethynyl Complexes in Aerated DMSO Solutions and Gels

Wan, Shigang; Lu, Wei

doi:10.1002/ange.201610762

Cited by 13 publications

(2 citation statements)

References 17 publications

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“…A similar effect of local molecular oxygen depletion on a photoreaction has recently been reported for the photoactivation of gold(I) arylethynyl complexes phosphorescence. 28 The ability of groundstate oxygen to quench the photorelease process also suggests that the reaction proceeds from the triplet excited state.…”

Section: Photoproductsmentioning

confidence: 99%

Porphyrin as a Versatile Visible-Light-Activatable Organic/Metal Hybrid Photoremovable Protecting Group

Sekhar

Chitose

Janoš

et al. 2021

Preprint

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Photoremovable protecting groups (PPGs) represent one of the main contemporary implementations of photochemistry in diverse fields of research and practical applications. For the past half century, organic and metal-complex PPGs were considered mutually exclusive classes, each of which providing unique sets of physical and chemical properties thanks to their distinctive structures. Here, we introduce the meso-methylporphyrin group as a prototype hybrid-class PPG that unites traditionally exclusive elements of organic and metal-complex PPGs within a single structure. We show that the porphyrin scaffold allows extensive modularity by functional separation of the metal-binding chromophore and up to four sites of leaving group release. The insertion of metal ions can be used to tune their spectroscopic, photochemical, and biological properties. We provide a detailed description of the photoreaction mechanism studied by steady-state and transient absorption spectroscopies and quantum-chemical calculations. Our approach applied herein could facilitate access to a hitherto untapped chemical space of potential PPG scaffolds.

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Section: Photoproductsmentioning

confidence: 99%

Porphyrin as a Versatile Visible-Light-Activatable Organic/Metal Hybrid Photoremovable Protecting Group

Sekhar

Chitose

Janoš

et al. 2021

Preprint

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“…Amongst various metal complex systems, alkynylgold(I) complexes with two‐coordinate linear geometry have been shown to possess rich photophysical properties and have been extensively studied 24–35 . Some of these alkynylgold(I) complexes are stable in ambient conditions to serve as metal‐containing functional materials for various applications, including luminescent materials, 36–40 cation sensors, 41,42 optical power limiting materials, 43 and more recently, resistive memory devices 15 and multi‐stimuli‐responsive materials 15,44 …”

Section: Introductionmentioning

confidence: 99%

Synthesis of benzo[b]phosphole‐based alkynylgold(I) complexes with resistive memory properties modulated by donor–acceptor chromophores

et al. 2021

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A class of benzo[b]phosphole‐based alkynylgold(I) complexes has been synthesized and characterized. These complexes share a similar benzo[b]phosphole ligand, in which the phosphole moiety is substituted with various π‐conjugated units with different donor strengths, namely phenoxazinylphenyl, tris(di‐tert‐butylcarbazolyl)phenyl and 2,4‐dimethylphenyl moieties. These phosphole‐containing gold(I) complexes are found to be strongly luminescent in toluene with tunable emission maxima and possess solvatochromic behaviors, suggesting an emission of metal‐perturbed intraligand charge transfer origin. Cyclic voltammetry studies reveal that the presence of gold(I) metal center strongly perturbs the electronic properties of the phosphole moiety of the resultant complexes, which can be further fine‐tuned by the auxiliary ligand on the gold(I) center. In the resistive memory studies, devices based on these alkynylgold(I) complexes exhibit satisfactory binary memory behaviors, demonstrating low threshold voltages in narrow distributions, high durability and low misreading rates. Such performances are believed to be originated from a field‐induced charge transfer of the alkynylgold(I) complexes, in which the electron‐accepting phosphole‐gold(I) unit plays a crucial role in stabilizing the charge transfer state and that led to the observed resistive switching and memory behavior.

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Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals

et al. 2019

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Herein we report a crystalline molecular rotor with rotationally modulated triplet emission that displays macroscopic dynamics in the form of crystal moving and/or jumping, also known as salient effects. Molecular rotor 2 with a central 1,4‐diethynyl‐2,3‐difluorophenylene rotator linked to two gold(I) nodes, crystalizes as infinite 1D chains through intermolecular gold(I)–gold(I) interactions. The rotational motion changes the orientation of the central phenylene, changing the electronic communication between adjacent chromophores, and thus the emission intensities. Crystals of 2 showed the large and reversible thermal expansion/compression anisotropy, which accounts for 1) a nonlinear Arrhenius behavior in molecular‐level rotational dynamics, which correlates with 2) changes in emission, and determines 3) the macroscopic crystal motion. A molecular rotor analogue 3 has properties similar to those of 2, suggesting a generalized way to control mechanical properties at molecular and macroscopic scales.

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Reversible Photoactivated Phosphorescence of Gold(I) Arylethynyl Complexes in Aerated DMSO Solutions and Gels

Cited by 13 publications

References 17 publications

Porphyrin as a Versatile Visible-Light-Activatable Organic/Metal Hybrid Photoremovable Protecting Group

Porphyrin as a Versatile Visible-Light-Activatable Organic/Metal Hybrid Photoremovable Protecting Group

Synthesis of benzo[b]phosphole‐based alkynylgold(I) complexes with resistive memory properties modulated by donor–acceptor chromophores

Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals

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