ピレン多量体の合成と官能基化、および円偏光発光挙動に関する研究

首都大学東京, 2018-9-30, 博士（理学）, 甲第835号首都大学東

High Rectification Ratio at Room Temperature in Rhenium(I) Compound

Electrical current rectification is an interesting electronic feature, popularly known as a diode. Achieving a high rectification ratio in a molecular junction has been a long-standing goal in molecular electronics. The present work describes mimicking electrical current rectification with pi-stacked rhenium(I) compound sandwiched between two electrical contacts. Among the two mononuclear rhenium compounds studied here, [Re(CO)4(PPh3){(N)-saccharinate}] (1) and [Re(CO)3(phen){(N)-saccharinate}] (2), the latter show strong pi-pi interactions-induced high rectification ratio of ~ 4000 at 2.0 V at room temperature. Alternating current (AC)-based electrical measurements ensuring AC to DC electrical signal conversion at a frequency f of 1 KHz showing 2 can act as an excellent half-wave rectifier. Asymmetric charge injection barrier height at the electrode/Re(I) interfaces of the devices with a stacking configuration of p++-Si/Re compound31nm(2)/ITO originates the flow of electrical current unidirectionally. The charge transport mechanism governed by thermally activated hopping phenomena, and charge carrier propagation is explained through an energy profile considering the Fermi levels of two electrodes, and the energy of frontier molecular orbitals, HOMO, and LUMO, confirming rectification is of a molecular origin. The present work paves the way to combine different organometallic compounds as circuit elements in nanoelectronic devices to achieve numerous exciting electronic features.Comment: 16 pages, 5 figure

<span style="font-size:13.0pt;font-family: "Times New Roman";mso-fareast-font-family:"Times New Roman";mso-bidi-font-family: Mangal;letter-spacing:-.3pt;mso-ansi-language:EN-GB;mso-fareast-language:EN-US; mso-bidi-language:HI" lang="EN-GB">Reaction of electron-deficient triosmium cluster Os₃(CO)₈{μ₃-Ph₂PCH(CH₃)P(Ph)C₆H₄}(μ-H) with HCl: X-ray structure of two isomers of Os₃(CO)₈{μ-Ph₂PCH(CH₃)PPh₂}(μ-Cl)(μ-H)</span>

1104-1108Treatment of electron-deficient Os3(CO)8{μ3-Ph2PCH(CH3)-P(Ph)C6H4}(μ-H) (1) with HCl at room temperature furnishes the adduct Os3(CO)8{μ-Ph2PCH(CH3)PPh2}(μ-Cl)(μ-H) (2) in almost quantitative yield via oxidative addition of H‒Cl bond. Cluster (2) is electron-precise and contains bridging chloride and hydride ligands which rearranges upon heating at 110 °C to form isomeric (3). Both clusters have been characterized by a combination of elemental analyses, IR and NMR spectroscopic data together with single crystal X-ray diffraction studies. </span

<span style="font-size:11.0pt;font-family: "Times New Roman";mso-fareast-font-family:"Times New Roman";mso-bidi-font-family: Mangal;mso-ansi-language:EN-GB;mso-fareast-language:EN-US;mso-bidi-language: HI" lang="EN-GB">Synthesis, structure and reactivity of triosmium clusters derived from the reactions of [Os₃(CO)₁₀(µ-dppm)] and <span style="font-size:11.0pt;font-family:"Times New Roman";mso-fareast-font-family: "Times New Roman";mso-bidi-font-family:Mangal;mso-ansi-language:PT-BR; mso-fareast-language:EN-US;mso-bidi-language:HI" lang="PT-BR">[(<span style="font-size:11.0pt;font-family:"Times New Roman";mso-fareast-font-family: "Times New Roman";mso-bidi-font-family:Mangal;mso-ansi-language:EN-GB; mso-fareast-language:EN-US;mso-bidi-language:HI" lang="EN-GB">µ<span style="font-size:11.0pt;font-family:"Times New Roman";mso-fareast-font-family: "Times New Roman";mso-bidi-font-family:Mangal;mso-ansi-language:PT-BR; mso-fareast-language:EN-US;mso-bidi-language:HI" lang="PT-BR">-H)Os₃(CO)₈{<span style="font-size:11.0pt;font-family:"Times New Roman";mso-fareast-font-family: "Times New Roman";mso-bidi-font-family:Mangal;mso-ansi-language:EN-GB; mso-fareast-language:EN-US;mso-bidi-language:HI" lang="EN-GB">µ_{<span style="font-size:11.0pt;font-family:"Times New Roman";mso-fareast-font-family: "Times New Roman";mso-bidi-font-family:Mangal;mso-ansi-language:PT-BR; mso-fareast-language:EN-US;mso-bidi-language:HI" lang="PT-BR">3</span>}<span style="font-size:11.0pt;font-family:"Times New Roman";mso-fareast-font-family: "Times New Roman";mso-bidi-font-family:Mangal;mso-ansi-language:PT-BR; mso-fareast-language:EN-US;mso-bidi-language:HI" lang="PT-BR">-Ph₂PCH₂P(Ph)C₆H₄}] <span style="font-size:11.0pt;font-family:"Times New Roman"; mso-fareast-font-family:"Times New Roman";mso-bidi-font-family:Mangal; mso-ansi-language:EN-GB;mso-fareast-language:EN-US;mso-bidi-language:HI" lang="EN-GB">with tris(<span style="font-size:12.0pt;mso-fareast-font-family: "Times New Roman";mso-bidi-font-family:"Times New Roman";mso-ansi-language: EN-GB;mso-fareast-language:EN-US;mso-bidi-language:HI;font-style:normal; mso-bidi-font-style:italic" lang="EN-GB">4<span style="font-size: 11.0pt;font-family:"Times New Roman";mso-fareast-font-family:"Times New Roman"; mso-bidi-font-family:Mangal;mso-ansi-language:EN-GB;mso-fareast-language:EN-US; mso-bidi-language:HI" lang="EN-GB">-fluorophenyl)phosphine and tris(cyanoethyl)phosphine</span></span></span></span></span></span></span></span></span>

581-587The reactions of [Os3(CO)10(µ-dppm)] (1) with tris(4-fluorophenyl)phosphine, P(4-FC6H4)3, and tris(cyanoethyl) phosphine, P(CH2CH2CN)3, in the presence of Me3NO in refluxing dichloromethane give the mono-substituted clusters [Os3(CO)9(µ-dppm){P(4-FC6H4)3)}] (2) and [Os3(CO)9(µ-dppm){P(CH2CH2CN)3)}] (3), respectively, in which the phosphine is bound to the non-dppm-substituted osmium center. The 46-electron compound [(µ-H)Os3(CO)8- {µ<span style="mso-ansi-language: PT-BR" lang="PT-BR">3-Ph2PCH2P(Ph)C6H4}] (6) reacts with an excess of P(4-FC6H4)3 and P(CH2CH2CN)3 at ambient temperature to yield (2) and (3), respectively. Heating (2) or (3)<b style="mso-bidi-font-weight: normal"> in refluxing toluene at 110 oC afforded the electron-deficient clusters [(µ-H)- Os3(CO)7{µ3-Ph2PCH2PPh(C6H4)}{P(4-FC6H4)3)}] (4) and [(µ-H)Os3(CO)7{µ3-Ph2PCH2PPh(C6H4)}{P(CH2CH2CN)3}] (5) resulting from C-H bond scission of the coordinated dppm and metal hydride bond formation. The molecular structures of (2), (3) and (<b style="mso-bidi-font-weight: normal">4) have been determined by single- crystal X-ray diffraction studies. </span

Synthesis and characterization of tungsten carbonyl complexes containing thioamides

274-280Tungsten pentacarbonyl complexes are isolated from the reactions between [W(CO)5(NCMe)] and thioamides, the former being generated in situ upon addition of  equimolar amount of Me3NO into an acetonitrile solution of W(CO)6. Room temperature reactions between [W(CO)5(NCMe)] and acyclic thioamides such as thioacetamide and benzamide afford [W(CO)5{к1-(S)-RCSNH2}] in which the thioamides are coordinated to tungsten through sulfur. Similar S-coordinated complexes, namely, [W(CO)5{к1-(S)-thiolactam}] are also isolated from the reactions with cyclic thioamides or thiolactams under the same reaction conditions. All the new complexes have been adequately characterized by spectroscopic data together with single crystal X-ray diffraction studies for four complexes

<span style="font-size:11.0pt;font-family: "Times New Roman";mso-fareast-font-family:"Times New Roman";mso-bidi-font-family: Mangal;color:black;mso-ansi-language:EN-GB;mso-fareast-language:EN-US; mso-bidi-language:HI" lang="EN-GB">New tertiary phosphine derivatives of Os₃(CO)₁₂: X-ray structures of 1,2-[Os₃(CO)₁₀{PhP(<i style="mso-bidi-font-style:normal">o</i>-Tol)₂}₂], 1,2,3-[Os₃(CO)₉{(4-FC₆H₄)₃P}₃], 1,2,3-[Os₃(CO)₉{PhP(Cy)₂}₃] and [Os₃(µ-OH)₂(CO)₈{(4-FC₆H₄)₃P}₂]</span>

161-169Reactions of 1,2-[Os3(CO)10(NCMe)2] (1) with tertiary phosphines such as tris(4-fluorophenyl)phosphine (4-FC6H4)3P, bis(<i style="mso-bidi-font-style: normal">o-tolyl)(phenyl)phosphine PhP(o-Tol)2 and dicyclohexyl(phenyl)phosphine PhP(Cy)2 have been examined at room temperature and found to yield the di- and tri-substituted products 1,2-[Os3(CO)10(PR3)2] {(2<span style="mso-bidi-font-weight: bold">), PR3 = (4-FC6H4)3P; (3<span style="mso-bidi-font-weight: bold">), PR3 = PhP(o-Tol)2; (4<span style="mso-bidi-font-weight: bold">), PR3 = PhP(Cy)2} and 1,2,3-[Os3(CO)9(PR3)3] {(5), PR3 = (4-FC6H4)3P; (6<span style="mso-bidi-font-weight: bold">), PR3 = PhP(o-Tol)2; 7, PR3 = PhP(Cy)2} as the major products, in addition to the dihydroxyl-bridged complexes 1,2-[Os3(CO)8(PR3)2(µ-OH)2] {(8<span style="mso-bidi-font-weight: bold">), PR3 = (4-FC6H4)3P; (9<span style="mso-bidi-font-weight: bold">), PR3 = PhP(o-Tol)2; (10<span style="mso-bidi-font-weight: bold">), PR3 = PhP(Cy)2} in trace amounts. Compounds (<b style="mso-bidi-font-weight: normal">2)-(10<span style="mso-bidi-font-weight: bold">) have been characterized by a combination of elemental analyses, infrared, NMR and mass spectral data together with single crystal X-ray diffraction studies for (3), (<b style="mso-bidi-font-weight: normal">5), (7<span style="mso-bidi-font-weight: bold">) and (8<span style="mso-bidi-font-weight: bold">). </span