Visualization of Ion Conductivity: Vapochromic Luminescence of an Ion-Conductive Ruthenium(II) Metalloligand-Based Porous Coordination Polymer

Watanabe, Ayako; Kobayashi, Atsushi; Saitoh, Erika; Nagao, Yuki; Yoshida, Masaki; Kato, Masako

doi:10.1021/acs.inorgchem.5b02077

Cited by 20 publications

(19 citation statements)

References 22 publications

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“…Absorption spectra showed that MOF exhibited efficient visible light harvesting with the absorption edge extended to around 650 nm due to the MLCT. The luminescence lifetime of MOF was 5.49 µs, which is more than one order of magnitude greater than that of [Ru] [234]. The coordination polymer exhibited a dark-red broad emission centered at 691 nm without any vibronic progressions, which is largely shifted to the longer wavelength than that of the 3 MLCT.…”

Section: Ligands Based On Highly Emissive Ruthenium(ii) and Iridium(iii) Complexesmentioning

confidence: 90%

Coordination Polymers Based on Highly Emissive Ligands: Synthesis and Functional Properties

et al. 2020

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Coordination polymers are constructed from metal ions and bridging ligands, linking them into solid-state structures extending in one (1D), two (2D) or three dimensions (3D). Two- and three-dimensional coordination polymers with potential voids are often referred to as metal-organic frameworks (MOFs) or porous coordination polymers. Luminescence is an important property of coordination polymers, often playing a key role in their applications. Photophysical properties of the coordination polymers can be associated with intraligand, metal-centered, guest-centered, metal-to-ligand and ligand-to-metal electron transitions. In recent years, a rapid growth of publications devoted to luminescent or fluorescent coordination polymers can be observed. In this review the use of fluorescent ligands, namely, 4,4′-stilbenedicarboxylic acid, 1,3,4-oxadiazole, thiazole, 2,1,3-benzothiadiazole, terpyridine and carbazole derivatives, naphthalene diimides, 4,4′,4′′-nitrilotribenzoic acid, ruthenium(II) and iridium(III) complexes, boron-dipyrromethene (BODIPY) derivatives, porphyrins, for the construction of coordination polymers are surveyed. Applications of such coordination polymers based on their photophysical properties will be discussed. The review covers the literature published before April 2020.

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Section: Ligands Based On Highly Emissive Ruthenium(ii) and Iridium(iii) Complexesmentioning

confidence: 90%

Coordination Polymers Based on Highly Emissive Ligands: Synthesis and Functional Properties

et al. 2020

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“…They have also found applications in novel solar cell functional materials [56], the reduction of carbon dioxide [57][58][59], etc. Additionally, inorganic chemists have utilized inorganic photocatalysts for functional components, viz, doping [60][61][62][63][64][65][66][67], encapsulated guests [68][69][70][71][72][73][74], molecular machines [75][76][77][78], for light harvesting, etc. [79].…”

Section: Review Why Photoredox Catalysis?mentioning

confidence: 99%

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

Siddiqui¹,

Ali²

2020

Beilstein J. Org. Chem.

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In recent years, the research area of direct C–H bond functionalizations was growing exponentially not only due to the ubiquity of inert C–H bonds in diverse organic compounds, including bioactive natural and nonnatural products, but also due to its impact on the discovery of pharmaceutical candidates and the total synthesis of intricate natural products. On the other hand, more recently, the field of photoredox catalysis has become an indispensable and unparalleled research topic in modern synthetic organic chemistry for the constructions of challenging bonds, having the foremost scope in academia, pharmacy, and industry. Therefore, the development of green, simpler, and effective methodologies to accomplish direct C–H bond functionalization is well overdue and highly desirable to the scientific community. In this review, we mainly highlight the impact on, and the utility of, photoredox catalysts in inert ortho and para C–H bond functionalizations. Although a surge of research papers, including reviews, demonstrating C–H functionalizations have been published in this vital area of research, to our best knowledge, this is the first review that focuses on ortho and para C–H functionalizations by photoredox catalysis to provide atom- and step-economic organic transformations. We are certain that this review will act as a promoter to highlight the application of photoredox catalysts for the functionalization of inert bonds in the domain of synthetic organic chemistry.

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“…Since water molecules are generally contributable to the proton conduction in most of the low-temperature proton conductors in both the vehicle and Grotthus mechanisms, the incorporation of water-sensitive molecular luminophores could be an effective approach to evaluate the proton conductivity through the luminescence. We recently reported that the luminescent coordination polymers Ln 7 -[RuC] 4 , which are composed of Ru(II) metalloligands functionalized with six carboxy groups, RuC (Scheme a; H 6 RuC = [Ru(H 2 dcbpy) 3 ] 2+ ; H 2 dcbpy = 2,2′-bipyridine-4,4′-carboxylic acid), and bridging lanthanide cations (Ln 3+ = La 3+ , Ce 3+ , or Nd 3+ ) exhibit interesting relative humidity (RH)-dependent cooperative behavior between the ion conductivity and the 3 MLCT emission energy of the RuC metalloligand. , This system could be used as a smart sensor for the evaluation of ion conductivity via the 3 MLCT emission energy, but the ion conductivity is poor, even at 100% RH (ca. 10 –6 S cm –1 ), and the shift in the 3 MLCT energy is small.…”

Section: Introductionmentioning

confidence: 99%

Two-Step Vapochromic Luminescence of Proton-Conductive Coordination Polymers Composed of Ru(II)-Metalloligands and Lanthanide Cations

et al. 2019

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Two proton-conductive and phosphorescent porous coordination polymers, La 3 -[H 5.5 RuP] 2 and Pr 3 -[H 5.5 RuP] 2 (H 12 RuP = [Ru(H4dpbpy)3]2+, H4dpbpy = 2,2′-bipyridine-4,4′-bis(phosphonic acid), composed of Ru(bpy)3-type metalloligands (bpy = 2,2′-bipyridine) functionalized with six phosphonate groups and lanthanide cations (Ln3+ = La3+ or Pr3+) were successfully synthesized. X-ray diffraction studies revealed that six to seven protons of the H 12 RuP metalloligand were removed in the coordination polymerization reaction to form the porous coordination framework (Ln 3 -[H 5.5 RuP] 2 ) with Ln3+ cations (Ln3+ = La3+ or Pr3+). Although their porous structures collapsed on the removal of water molecules from the porous channels, the original porous structures were reconstructed by water adsorption. Interestingly, the triplet metal-to-ligand charge-transfer (3MLCT) emission of Ln 3 -[H 5.5 RuP] 2 was blue-shifted on increasing the relative humidity (RH) in the low RH region, whereas the inverse red shift was observed in the high RH region, resulting in the highest-energy 3MLCT emission at medium RH. The origin of this two-step vapochromic luminescence (that is, the blue and red shifts of the 3MLCT emission) is ascribable to the water-adsorption-triggered reconstruction of the porous structure and the proton release from the H 5.5 RuP metalloligand to the water filled channels, respectively. The proton conductivity of Ln 3 -[H 5.5 RuP] 2 is about 1000-times higher at 20% RH and 10-times higher at 95% RH than that of the carboxylate analog, La 7 -[RuC] 4 (H 6 RuC = [Ru(H2dcbpy)3]2+; H2dcbpy = 2,2′-bipyridine-4,4′-bis(carboxylic acid)), probably because of the highly acidic phosphonic acid groups.

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Visualization of Ion Conductivity: Vapochromic Luminescence of an Ion-Conductive Ruthenium(II) Metalloligand-Based Porous Coordination Polymer

Cited by 20 publications

References 22 publications

Coordination Polymers Based on Highly Emissive Ligands: Synthesis and Functional Properties

Coordination Polymers Based on Highly Emissive Ligands: Synthesis and Functional Properties

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

Two-Step Vapochromic Luminescence of Proton-Conductive Coordination Polymers Composed of Ru(II)-Metalloligands and Lanthanide Cations

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