Thermostable Organo‐phosphor: Low‐Vibrational Coordination Polymers That Exhibit Different Intermolecular Interactions

Miyata, Kohei; Ohba, Tadashi; Kobayashi, Atsushi; Kato, Masako; Nakanishi, Takayuki; Fushimi, Koji; Hasegawa, Yasuchika

doi:10.1002/cplu.201200002

Cited by 63 publications

(80 citation statements)

References 54 publications

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“…The hfa (hexafluoroacetylacetonate) chelating ligand is also a good building unit for the construction of MOFs exhibiting strong emissions. Hasegawa and colleagues 60 reported the onedimensional Eu(III) coordination polymers, [Eu(hfa) 3 (L)] (L = bidentate phosphane oxide ligands). In particular, a high-emission quantum yield (Φ Ln = 83% in the solid state) was observed in [Eu(hfa) 3 (dppcz)] (dppcz = 3,6-bis(diphenylphosphoryl)-9-phenylcarbazole).…”

Section: Discussionmentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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Fluorine, the element with the highest electronegativity and low electric polarizability, can produce a variety of characteristics, including specific adsorption sites for molecules as well as flexibility to the host materials. In this review, we will introduce fluorine-functionalized metal-organic frameworks/porous coordination polymers that show unique and unprecedented structures, structural transformations, and gas and vapor adsorption/separation properties derived from the fluorine characteristics. NPG Asia Materials (2017) 9, e433; doi:10.1038/am.2017.165; published online 29 September 2017 INTRODUCTIONDuring the last two decades, metal-organic frameworks (MOFs)/ porous coordination polymers (PCPs) composed of metal ions and organic bridging ligands as main building units and, in some cases, inorganic ligands, have been investigated extensively because of their versatile structural diversity, high structural controllability (pore size, shape, dimension, flexibility and surface environment), high crystallinity, and their potential porous properties/functionalities in a variety of research fields such as storage and separation, catalysis, drug delivery and sensing ability. 1-3 The porous properties of MOFs/PCPs can be finely tailored by not only chemical modification of organic ligands and judicious choice of components but also a variety of techniques such as solid solution formation, defect engineering, core-shell structure, crystal morphology and size control, and so on. For example, the appropriate combination of organic bridging ligands provided the Zn(II) MOF, [Zn 4 O(bte) 4/3 (bpdc)] (bte = 4,4′,4′′-[benzene-1,3,5-triyl-tris (ethyne-2,1-diyl)]tribenzoate, bpdc = biphenyl-4,4′-dicarboxylate), with ultra-high Brunauer-Emmett-Teller and Langmuir specific surface areas close to 6000 and 10 000 m 2 g − 1 , respectively. 4 Unlike porous inorganic zeolites and porous carbon materials, MOFs often give flexible structures. As coordination bonds, hydrogen bonds and van der Waals interactions that are used to assemble each component are weaker (bonding energies are 10~200 kJ mol − 1 ) than covalent and ionic bonds (200~1000 kJ mol − 1 ), reversible rotation, bending and breaking of these weaker bonds easily occurs, resulting in structural changes. One representative of flexible MOFs is [Cr(OH)(1,4-bdc)] (MIL-53(Cr), 1,4-bdc = 1,4-benzenedicarboxylate), in which local reorientation of the coordination bond triggered by guest adsorption/ desorption induced the structural transformation between narrow pore and large pore forms. 5 In addition, many MOFs show high crystallinity as with porous inorganic zeolites, which is advantageous for understanding deeply the structure-property relationship using single-crystal and powder X-ray diffraction techniques. For example, the unprecedented highly selective CO sorption from a CO/N 2 mixture, which is

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Section: Discussionmentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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“…5b The intrinsic 4f-4f emission quantum yield of [Eu(hfa) 3 (dpbp) x (SDPO) y ] n and [Eu(hfa) 3 (dpbp) x (SDPO) y ] n -PS in the solid-state were also determined based on the emission lifetime with a single-exponential decay and 4f-4f transition probability (Table 1). 6 The 4f-4f emission quantum yield (Φ Ln )…”

Section: Emission Propertiesmentioning

confidence: 99%

“…6 A solution of n-BuLi (9.3 mL, 1.6 M hexane, 15 mmol), was added dropwise to a solution of 4,4'-dibromobiphenyl (1.9 g, 6.0 mmol) in dry THF (30 mL) at -80 o C. The addition was completed in ca. 15 min during which time a yellow precipitate was formed.…”

Section: Preparation Of 44'-bis(diphenylphosphoryl)biphenyl [Dpbp]mentioning

confidence: 99%

“…The lanthanide coordination polymers exhibit high emission quantum yield (quantum yield = 83 %). 6 The thermostable lanthanide coordination polymers are expected to be promising candidates for practical opto-electric devises and temperature-sensitive dyes. In particular, temperature-sensitive dyes under 300 o C are used for temperature distribution measurements of material surfaces such as an aerospace plane in wind tunnel experiments.…”

Section: Introductionmentioning

confidence: 99%

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Acid-protected Eu(iii) coordination nanoparticles covered with polystyrene

et al. 2016

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3 (dpbp) x (SDPO) y ] n were characterrized using ESI-Mass spectrometry (ESI-MS), X-Ray diffraction (XRD), Scanning electron microscopy (SEM), dynamic light scattering (DLS) measurements, and termogravimetric analysis (TGA). The [Eu(hfa) 3 (dpbp) x (SDPO) y ] n -PS shows effectively acidresistance property based on polystyrene layer on their nanoparticle surface. The emission intensity is kept under 3000s in acidic condition (pH = 0.92). In this study, acid-protected Eu(III) coordination nanoparticles are demonstrated. IntroductionLanthanide complexes with narrow emission bands and long emission lifetimes have been regarded as attractive luminescent materials for use in electroluminescent optical materials, 1 organic light-emitting diodes(OLEDs), 2 and luminescent biosensing applications. 3 At the present stage, various types of luminescent lanthanide complexes have been reported. 4 Lanthanide coordination polymer composed of lanthanide ions and organic joint ligands are also focused for new luminescent materials, 5 recently. Their tight packing structures promote effective thermo-stability and small non-radiative rate constant for strong luminescence. Our research group have reported thermostable lanthanide coordination polymers composed of lanthanide ions and organo-phosphine oxides (decomposition temperature > 300 o C). The lanthanide coordination polymers exhibit high emission quantum yield (quantum yield = 83 %). 6The thermostable lanthanide coordination polymers are expected to be promising candidates for practical opto-electric devises and temperature-sensitive dyes. In particular, temperature-sensitive dyes under 300 o C are used for temperature distribution measurements of material surfaces such as an aerospace plane in wind tunnel experiments. 7The lanthanide coordination polymers with tight-stacking structures, however, lead to formation of insoluble compounds, micro-sized particles, in water and organic solvents. The insoluble micro-sized particles cause multiple light scattering in UV-Vis region. The nanoparticles of lanthanide coordination polymers without multiple light scattering may increase transmission of optical and luminescent materials. We recently successfully reported that luminescent nanoparticles of lanthanide coordination polymers are prepared by addition of monodentate phosphine oxide (triphenyl phosphine oxide: TPPO) as a polymerization terminator. 8In order to improve for practical material applications, surface protection on the lanthanide coordination nanoparticles should be required for acidic condition of industrial manufacturing process. Generally, industrial plastic materials are prepared with acid generator such as benzoyl peroxide under water. ApparatusInfrared spectra were recorded with a JASCO FTIR-350 spectrometer.1 H NMR (400 MHz) spectra were recorded with a JEOL ECS400 spectrometer. Chemical shifts are reported in ppm and are referenced to an internal tetramethylsilane standard for 1 H NMR spectroscopy. Elemental analyses were performed with a Yanaco CNH MT-6 a...

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“…Based on their photophysical and chemical views, we report novel organophosphor compounds: coordination polymers composed of Eu(III) and three types of aryl units; [Eu(hfa) 3 (dpb)] n , [Eu(hfa) 3 (dpbp)] n (Figure 21), and [Eu(hfa) 3 -(dppcz)] n (dpb: 1,4-bis(diphenylphosphoryl)benzene, dpbp: 4,4¤-bis(diphenylphosphoryl)biphenyl, dppcz: 3,6-bis(diphenylphosphoryl)-9-phenylcarbazole). 136 Their thermal stabilities are characterized by thermogravimetric analyses (TGA and DSC). The decomposition points of [Eu(hfa) 3 (dpb)] n , [Eu(hfa) 3 -(dpbp)] n , and [Eu(hfa) 3 (dppcz)] n are found to be 261, 308, and 300°C, respectively.…”

Section: Luminescent Lanthanoid Complex V: Lanthanoid Coordination Pomentioning

confidence: 99%

Photofunctional Lanthanoid Complexes, Coordination Polymers, and Nanocrystals for Future Photonic Applications

Hasegawa

2014

Bulletin of the Chemical Society of Japan

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In this account, lanthanoid complexes, coordination polymers, and nanocrystals with photofunctional properties are introduced. To maintain the effective emission of Nd(III), Sm(III), Eu(III), Tb(III), and Yb(III) ions in organic media, the coordination sphere of the lanthanoid ions should consist of strong, bulky, and asymmetric ligands with low vibrational frequencies, that is, there are three criteria for luminescence: 1) suppression of vibrational relaxation, 2) prevention of nonradiative cross relaxation at diffusional collision, and 3) introduction of asymmetric coordination geometry for enhancing electric dipole transition. Lanthanoid coordination compounds with characteristic photosensitizing properties, photochromic properties, circularly polarized luminescence (CPL), metal ion sensing properties, solvent sensing properties, energy-conversion properties, thermostable properties, triboluminescent properties, and thermosensing properties are also described for the development of photofunctional materials. In the second half, the synthesis, photophysical magnetic, and magneto-optical properties of lanthanoid nanocrystals, EuO, EuS, and EuSe, are reported. In particular, the remarkable photophysical properties of nanoaggregates composed of EuS nanocrystals are presented. Photofunctional lanthanoid(III) complexes, coordination polymers, and nanocrystals are expected to open up a frontier field of materials science.

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Thermostable Organo‐phosphor: Low‐Vibrational Coordination Polymers That Exhibit Different Intermolecular Interactions

Cited by 63 publications

References 54 publications

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Acid-protected Eu(iii) coordination nanoparticles covered with polystyrene

Photofunctional Lanthanoid Complexes, Coordination Polymers, and Nanocrystals for Future Photonic Applications

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