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101.
Shekhah O Hirai K Wang H Uehara H Kondo M Diring S Zacher D Fischer RA Sakata O Kitagawa S Furukawa S Wöll C 《Dalton transactions (Cambridge, England : 2003)》2011,40(18):4954-4958
We report the successful heteroepitaxial growth of perfectly oriented hybrid MOF thin films. By employing step-by-step liquid-phase epitaxy (LPE), [Zn(2)(ndc)(2)(dabco)](n) was grown on [Cu(2)(ndc)(2)(dabco)](n), thus demonstrating that the MOF-on-MOF deposition scheme developed for powdered microcrystalline MOF materials can also be applied in connection with LPE for MOF thin films or multilayers. The deposition was monitored by surface plasmon resonance (SPR) spectroscopy, the resulting MOF heterostructures were characterized using IR spectroscopy and different types of X-ray diffraction (XRD)-based techniques. The results suggest that the LPE method is a promising way to fabricate and grow MOF heterostructures, and also demonstrates the potential of [Cu(2)(ndc)(2)(dabco)](n) MOF thin films as substrates for the LPE-based growth of different MOFs on top. 相似文献
102.
Copper-mediated chemoselective trifluoromethylation at the benzylic position by the use of shelf-stable electrophilic trifluoromethylating reagents 3 in good to high yields under mild conditions is described for the first time. The generality of this trifluoromethylation for a wide variety of benzyl bromides facilitates the rapid creation of structural diversity of medicinal candidates in drug discovery. 相似文献
103.
Ohtani R Yoneda K Furukawa S Horike N Kitagawa S Gaspar AB Muñoz MC Real JA Ohba M 《Journal of the American Chemical Society》2011,133(22):8600-8605
Precise control of spin transition temperature (T(c)) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt(II)(CN)(4)]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T(c)(up) = 304 K and T(c)(down) = 284 K) and its iodine adduct {Fe(pz)[Pt(II/IV)(CN)(4)(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt(II), raised the T(c) by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)(4)(I)(n)]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of T(c) in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate T(c) ad arbitrium through unique postsynthetic method using iodine migration. 相似文献
104.
Furukawa H Go YB Ko N Park YK Uribe-Romo FJ Kim J O'Keeffe M Yaghi OM 《Inorganic chemistry》2011,50(18):9147-9152
The concept and occurrence of isoreticular (same topology) series of metal-organic frameworks (MOFs) is reviewed. We describe the preparation, characterization, and crystal structures of three new MOFs that are isoreticular expansions of known materials with the tbo (Cu(3)(4,4',4'-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate)(2), MOF-399) and pto topologies (Cu(3)(4,4',4'-(benzene-1,3,5-triyl-tribenzoate)(2), MOF-143; Cu(3)(4,4',4'-(triazine-2,4,6-triyl-tris(benzene-4,1-diyl))tribenzoate)(2), MOF-388). One of these materials (MOF-399) has a unit cell volume 17 times larger than that of the first reported material isoreticular to it, and has the highest porosity (94%) and lowest density (0.126 g cm(-3)) of any MOFs reported to date. 相似文献
105.
Etou J Ino D Furukawa D Watanabe K Nakai IF Matsumoto Y 《Physical chemistry chemical physics : PCCP》2011,13(13):5817-5823
We have investigated the mechanism of enhanced absorption intensities of vibrational bands of adsorbates on copper meshes with subwavelength holes by measuring and simulating temporal profiles of infrared pulses transmitted through the meshes. As reported previously [Williams et al., J. Phys. Chem. B, 2003, 107, 11871], the absorption intensities of CH stretching bands of alkanethiolate adsorbed on the mesh increase substantially with decreasing hole size. The enhancements of absorption intensities are associated with temporal delays of infrared pulses transmitted through the mesh. Finite difference time domain calculations reproduce the observed pulse delays as a function of hole size. These facts indicate that the delays of transmitted pulses are not caused by coupling of infrared radiation to surface plasmon polaritons propagating on the front and rear surfaces of the mesh, but they are caused by the reduction in group velocity owing to coupling to waveguide modes of mesh holes. Consequently, the strong enhancements of the absorption intensities are attributed to adsorbates inside the holes rather than to those on the mesh surfaces that have been proposed previously. 相似文献
106.
Y. Furukawa H. Terao H. Ishihara T. M. Gesing J.-C. Buhl 《Hyperfine Interactions》2004,159(1-4):143-148
The crystal structure of [C(NH2)3]2HgBr4 has been determined at room temperature: monoclinic, space group C2/c, with a = 10.035(2), b = 11.164(2), c = 13.358(3) Å, β = 111.67(3)°, and Z = 4. The crystal consists of planar [C(NH2)3]+ and distorted tetrahedral [HgBr4]2? ions. The Hg atom is located on a two-fold axis such that two sets of inequivalent Br atoms exist in an [HgBr4]2? ion. In accordance with the crystal structure, two 81Br NQR lines widely separated in frequency were observed between 77 and ca. 380 K. [C(NH2)3]2HgI4 yielded four 127I NQR lines ascribable to m = ±1/2 ? ±3/2 transitions, indicating that its crystal structure is different from the bromide complex. The 1H NMR T 1 measurements showed a single minimum for the bromide but two minima for the iodide. The analyses based on the C3 reorientations of the planar [C(NH2)3]+ ions gave the activation energies of 29.8 kJ mol?1 for the bromide, and 30.2 and 40.0 kJ mol?1 for the iodide. 相似文献
107.
Akane Suzuki Daisuke Nagai Bungo Ochiai Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2004,42(23):5983-5989
The trifunctional five‐membered cyclic carbonate 2 and dithiocarbonate 3 were successfully synthesized by the reaction of trifunctional epoxide 1 with carbon dioxide and carbon disulfide, respectively. The crosslinking reactions of 2 with p‐xylylenediamine or hexamethylenediamine were carried out in dimethyl sulfoxide at 100 °C for 48 h to produce the corresponding crosslinked poly(hydroxyurethane)s quantitatively. The crosslinking reactions of 3 with both p‐xylylenediamine and hexamethylenediamine, followed by acetylation of thiol moiety, produced the corresponding crosslinked poly(thioester–thiourethane)s quantitatively. The obtained crosslinked poly(hydroxyurethane)s were thermally more stable than the analogous crosslinked poly(thioester–thiourethane)s, probably because of less thermal stability of thiourethane moiety than hydroxyurethane moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5983–5989, 2004 相似文献
108.
109.
110.
Ken Kojio Sadaharu Nakamura Mutsuhisa Furukawa 《Journal of Polymer Science.Polymer Physics》2008,46(19):2054-2063
The effect of side methyl and dimethyl groups of the soft segment component on the microphase‐separated structure and mechanical properties of polyurethane elastomers (PUEs) was investigated. Poly(oxytetramethylene) glycol (PTMG), and PTMG incorporating dimethyl groups (PTG‐X) and methyl side groups (PTG‐L) were used as a polymer glycol, which forms a soft segment in the PUEs. The PUEs were synthesized with 4,4′‐dipheylmethane diisocyanate [1,1′‐methylenebis(4‐isocyanatobenzene)], 1,4‐butane diol, and 1,1,1‐trimethylol propane by a prepolymer method. The degree of microphase separation of the PUEs became weaker with increasing side group content in polymer glycols. Dynamic viscoelastic properties measurement showed reorganized‐crystallization and melting of the soft segment for the PUEs based on PTMG, PTG‐L, and PTG‐X with a lower content of the side groups, but not for a PTG‐L and PTG‐X with higher content of the side groups. Tensile testing revealed that increasing methyl group concentration made the PUEs soften and weaken. The PTMG‐based PUEs obviously exhibited strain‐induced crystallization of the soft segment chains during elongation process. In contrast, for the PTG‐L and PTG‐X‐based PUEs, crystallinity decreased with increasing side group content, and the PUEs with PTG‐L and PTG‐X with highest methyl group content did not crystallize even at a large strain. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2054–2063, 2008 相似文献