Showing papers by "Shinji Inagaki published in 2020"

Lanthanide Grafted Bipyridine Periodic Mesoporous Organosilicas (BPy-PMOs) for Physiological Range and Wide Temperature Range Luminescence Thermometry

Abstract: 2,2'-Bipyridine is the most widely used chelating ligand for developing metal complexes in coordination and supramolecular chemistry. Here, we present a series of three bipyridine periodic mesoporous organosilicas (BPy-PMOs) grafted with lanthanide β-diketonate complex for the purpose of obtaining thermochromic materials, which can be employed as ratiometric temperature sensors. Such thermometers are based on the ratio of two emission intensity peaks and are not affected by factors such as alignment or optoelectronic drift of the excitation source and detectors. Three thermometric systems are studied: Dy-Dy, Tb-Sm, and Tb-Eu with the first two showing very attractive performance. For the first two systems, some of the best reported to date relative sensitivities are observed. In the BPy-PMO@Dy(acac)3 system, it is very unusual that the 4I15/2→ 6H15/2 transition is already occupied at low temperature such as 200 K, which influences its thermometric behavior. The Tb-Sm shows excellent performance in the physiological range and when suspended in water. We have additionally confirmed that the BPy-PMO hybrid materials lack toxicity to human cells, proving them very promising candidates for biomedical thermometric applications.

Hydrogen Production from Methanol-Water Mixture over Iridium Complex-Immobilized Catalysts in Vapor-Phase Flow Reaction

Abstract: CO-free hydrogen production from methanol and water, using transition metal complex catalysts, has attracted increasing attention. However, liquid-phase batch reactions using homogeneous catalysts are impractical for large-scale operations owing to the consumption of bases and the use of organic solvents or additives. Herein, we report a novel method for continuous hydrogen production from a simple methanol-water solution under vapor-phase flow. The reaction was catalyzed by an anionic iridium-bipyridonate (Ir-bpyd) complex immobilized on a periodic mesoporous organosilica. Liquid-phase batch reaction using homogeneous anionic Ir-bpyd complex was immediately deactivated due to CO 2 generation, whereas no catalyst deactivation was observed in the vapor-phase flow reaction because CO 2 was smoothly removed from the catalyst bed, enabling continuous hydrogen production without the addition of a base. Thus, the critical problems pertaining to homogeneous catalysts were successfully overcome.

Iridium Complex Immobilized on Custom-Designed Periodic Mesoporous Organosilica as Reusable Catalyst for the Dehydrogenative Oxidation of Alcohols

Abstract: Over the past few decades, a number of homogeneous transition metal complex catalysts for efficient organic transformations have been developed. Some of these highly active catalysts have been desi...

Ab initio study on the excited states of pyrene and its derivatives using multi-reference perturbation theory methods

Abstract: Low-lying singlet excited states of pyrene derivatives originated from the 1La and 1Lb states of pyrene have decisive influences on their absorption and fluorescence emission behaviors. Calculation of these excited states with quantitative accuracy is required for the theoretical design of pyrene derivatives tailored to target applications; this has been a long-standing challenge for ab initio quantum chemical calculations. In this study, we explore an adequate computational scheme through calculations of pyrene and its phenyl-substituted derivatives using multi-reference perturbation theory (MRPT) methods. All valence π orbitals on the pyrene moiety were assigned to the active orbitals. Computational load was reduced by restricting the electron excitations within the active orbitals in the preparation of reference configuration space. A generalized multi-configuration quasi-degenerate perturbation theory (GMCQDPT) was adopted to treat the reference space other than the complete active space. The calculated 1La and 1Lb excitation energies of pyrene are in good agreement with the experimental values. Calculations of 1,3,6,8-tetraphenyl pyrene suggest that the energetic ordering of 1La and 1Lb is inverted through tetraphenyl substitution and its lowest singlet excited state is the 1La parentage of pyrene, which is consistent with the experimentally deduced scheme. These results are not readily obtained by MRPT calculations with a limited number of active orbitals and single-reference theory calculations. Diphenyl pyrenes (DPPy) were also calculated at the same level of theory to investigate the dependence on the substitution positions of phenyl groups.

Heterogeneous water oxidation photocatalysis based on periodic mesoporous organosilica immobilizing a tris(2,2′-bipyridine)ruthenium sensitizer

Abstract: A periodic mesoporous organosilica (PMO) containing 2,2′-bipyridine groups (BPy-PMO) has been shown to possess a unique pore wall structure in which the 2,2′-bipyridine groups are densely and regularly packed. The surface 2,2′-bipyridine groups can function as chelating ligands for the formation of metal complexes, thus generating molecularly-defined catalytic sites that are exposed on the surface of the material. We here report the construction of a heterogeneous water oxidation photocatalyst by immobilizing several types of tris(2,2′-bipyridine)ruthenium complexes on BPy-PMO where they function as photosensitizers in conjunction with iridium oxide as a catalyst. The Ru complexes produced on BPy-PMO in this work were composed of three bipyridine ligands, including the BPy in the PMO framework and two X2bpy, denoted herein as Ru(X)-BPy-PMO where X is H (2,2′-bipyridine), Me (4,4′-dimethyl-2,2′-bipyridine), t-Bu(4,4′-di-tert-butyl-2,2′-bipyridine) or CO2Me (4,4′-dimethoxycarbonyl-2,2′-bipyridine). Efficient photocatalytic water oxidation was achieved by tuning the photochemical properties of the Ru complexes on the BPy-PMO through the incorporation of electron-donating or electron-withdrawing functionalities. The reaction turnover number based on the amount of the Ru complex was improved to 20, which is higher than values previously obtained from PMO systems acting as water oxidation photocatalysts.

Direct nanoimprinting of nanoporous organosilica films consisting of covalently crosslinked photofunctional frameworks

Abstract: Nanoimprinting methods have been used widely to prepare various patterned or nanostructured thin films from inorganic or organic components. However, the accumulation of large functional aromatic groups in covalently crosslinked nanoimprints is challenging, due to the difficulty in controlling the fluidity and reactivity of the precursor films. In this work, nanoimprinting of naphthalimide-silica sol-gel films results in vertically oriented nanoporous structures consisting of covalently crosslinked UV-absorbing frameworks. The nanoimprinted films demonstrate potential as robust analytical substrates for laser desorption/ionization mass spectrometry (LDI-MS). The sol-gel polycondensation behavior of the precursors is examined using 29Si NMR spectroscopy to determine reaction conditions suitable for nanoimprinting. The inorganic-organic hybrid frameworks containing a high density of naphthalimide groups exhibit small volume shrinkage during the polycondensation reactions, which leads to desired nanoimprinting. Various bio-related compounds on the order of picomole to femtomole quantities are detectable by LDI-MS measurements using the nanoimprinted substrates. To improve their user-friendliness and signal intensity in LDI-MS analysis, the nanoimprinted substrates are patterned with surface-modified silica nanoparticles. The direct formation of surface nanostructures by nanoimprinting of functional organosilica films may open a new path to developing optically and electronically functional materials, thereby widening their utility.