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Koide, Taro,Furukawa, Ko,Shinokubo, Hiroshi,Shin, Jae-Yoon,Kim, Kil Suk,Kim, Dongho,Osuka, Atsuhiro American Chemical Society 2010 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.132 No.21
<P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2010/jacsat.2010.132.issue-21/ja101040s/production/images/medium/ja-2010-01040s_0006.gif'> <P>A <I>meso</I>,<I>meso</I>-diketohexaphyrin was isolated and characterized as a chemically stable non-Kekulé singlet biradicaloid. Two unpaired electrons are seemingly delocalized on two tripyrrolic units separated by C?O bonds. These results underscore the potential of expanded porphyrins to achieve unique electronic states.</P></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja101040s'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja101040s'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja101040s'>ACS Electronic Supporting Info</A></P>
Faialaga, Nathan H.,Ito, Satoru,Shinokubo, Hiroshi,Kim, Younghoon,Kim, Kimoon,Shin, Ji-Young The Royal Society of Chemistry 2017 Dalton transactions Vol.46 No.33
<▼1><P>Ni<SUP>II</SUP>-Metallation of dicyanovinylene-bis(<I>meso</I>-aryl)dipyrrin 1 under refluxed toulene conditions resulted in the formation of a bicyclic pyrrolizine ring to afford two isomeric bisNi<SUP>II</SUP> expanded porphyrinoid complexes 2a and 2b, which exhibited typical features of aromatic porphyrinoids.</P></▼1><▼2><P>Ni<SUP>II</SUP>-Metallation of dicyanovinylene-bis(<I>meso</I>-aryl)dipyrrin 1 under refluxed toulene conditions resulted in the formation of a bicyclic pyrrolizine ring to afford two isomeric bisNi<SUP>II</SUP> expanded porphyrinoid complexes 2a and 2b. Furthermore, acyclic Ni<SUP>II</SUP> dipyrrin complex 3 was also isolated. The respective structures for 2a, 2b, and 3 were elucidated by X-ray diffraction analysis. Macrocycles 2a and 2b exhibited typical features of aromatic porphyrinoids showing their longest wavelength absorption bands in the near infrared region ranging from 1100 to 1600 nm.</P></▼2>
Rath, Harapriya,Aratani, Naoki,Lim, Jong Min,Lee, Jae Seok,Kim, Dongho,Shinokubo, Hiroshi,Osuka, Atsuhiro Royal Society of Chemistry 2009 Chemical communications Vol.2009 No.25
<P>Metalation of [28]hexaphyrin(1.1.1.1.1.1) with [RhCl(CO)<SUB>2</SUB>]<SUB>2</SUB> resulted in the formation of an antiaromatic bis-Rh(<SMALL>I</SMALL>) complex, which can be oxidized to an aromatic bis-Rh(<SMALL>I</SMALL>) complex with retention of its rectangular structure.</P> <P>Graphic Abstract</P><P>Metalation of [28]hexaphyrin(1.1.1.1.1.1) with [RhCl(CO)<SUB>2</SUB>]<SUB>2</SUB> resulted in the formation of an antiaromatic bis-Rh(<SMALL>I</SMALL>) complex. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b905859a'> </P>
Porphyrin “Lego Block” Strategy To Construct Directly meso–β Doubly Linked Porphyrin Rings
Song, Jianxin,Aratani, Naoki,Kim, Pyosang,Kim, Dongho,Shinokubo, Hiroshi,Osuka, Atsuhiro WILEY-VCH Verlag 2010 Angewandte Chemie Vol.122 No.21
<B>Graphic Abstract</B> <P>Eingerastet: Die Suzuki-Miyaura-Kupplung von β,β′-diborylierten mit meso,meso′-dibromierten Porphyrinblöcken wird für den Aufbau direkt doppelt meso-β-verknüpfter Porphyrinringe genutzt, darunter zweier Tetraporphyrinringe, Hexaporphyrinringe und eines verbrückten Heptaporphyrins (siehe Bild). <img src='wiley_img_2010/00448249-2010-122-21-ANGE201000915-content.gif' alt='wiley_img_2010/00448249-2010-122-21-ANGE201000915-content'> </P>
Cho, Sung,Lim, Jong Min,Hiroto, Satoru,Kim, Pyosang,Shinokubo, Hiroshi,Osuka, Atsuhiro,Kim, Dongho American Chemical Society 2009 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.131 No.18
<P>Directly and doubly beta,beta'-linked corrole dimers (DH(3)CD, DH(2)CD, and DZnCD) are excellent platforms for the investigation of intercorrole interactions because of their enforced coplanar geometries and short edge-to-edge distances. Through the use of these molecules along with the reference monomer H(3)CM and the singly beta,beta'-linked corrole dimer SH(3)CD, the intercorrole interactions have been systematically studied by density functional theory calculations, ultrafast photophysical measurements, and two-photon absorption measurements. A particular focus was placed on revealing factors that are important for the induced photophysical properties of the doubly linked corrole dimers compared with corrole monomer. In the doubly linked corrole dimers, strong molecular orbital interactions caused by the coplanar geometry and the short interchromophoric distance give rise to perturbations of the electronic states that are responsible for the red-shifted and intensified Q-like band in DH(3)CD and the broad NIR absorption bands and fast excitation-energy relaxation processes in DH(2)CD and DZnCD. On the other hand, electronic communication between corrole units is prohibited by the structurally constrained octagonal core in the center, so each constituent corrole unit in the doubly linked corrole dimers maintains an intrinsic pi-conjugation system. Consequently, the overall aromaticity of the directly linked corrole dimers can be explained in terms of a linear sum of two constituent corrole monomers, and the singlet biradical character of DH(2)CD and DZnCD can be understood in terms of two unpaired electrons (one from each constituent oxidized corrole monomer) and their appropriate interaction. In addition, the nonlinear optical properties of DH(2)CD and DZnCD with singlet biradical character have been confirmed to be significantly enhanced compared with those of closed-shell DH(3)CD. Collectively, double beta,beta'-linkages of corroles provide the coplanar geometry with a short interchromophoric distance and the strained octagonal core that play key roles in allowing the strong molecular orbital interactions and restricting the electronic communication between the two corroles, respectively.</P>
Azabuckybowl-Based Molecular Tweezers as C<sub>60</sub> and C<sub>70</sub> Receptors
Takeda, Motoki,Hiroto, Satoru,Yokoi, Hiroki,Lee, Sangsu,Kim, Dongho,Shinokubo, Hiroshi American Chemical Society 2018 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.140 No.20
<P>We designed and synthesized molecular tweezers consisting of nitrogen-embedded buckybowl subunits. The judicious choice of the covalent linkers modulated their binding strength with C<SUB>60</SUB> or C<SUB>70</SUB> in solution. Titration studies by optical and <SUP>1</SUP>H NMR analyses revealed a 1:1 composition of the resulting complexes. X-ray diffraction analysis elucidated their solid-state structures, in which two azabuckybowl units surround one fullerene molecule. The large association constants stabilize the complexes toward redox reactions and the purification process on silica-gel column chromatography. The linker enabled tuning of the cavity size for binding of fullerenes, achieving complementary fullerene hosts for C<SUB>60</SUB> and C<SUB>70</SUB>: the carbazole-bridged dimer preferentially associates with C<SUB>70</SUB> over C<SUB>60</SUB>, while the phenanthrene-bridged dimer interacts with C<SUB>60</SUB> more strongly than C<SUB>70</SUB>. Electrochemical analysis in combination with density functional theory calculations indicated the existence of intermolecular charge-transfer interactions between the buckybowl units and the fullerenes. Nonlinear optical measurements showed that the two-photon absorption cross sections of the molecular tweezers are enhanced upon association with fullerenes.</P> [FIG OMISSION]</BR>
Strategic Synthesis of 2,6-Pyridylene-Bridged β-to-β Porphyrin Nanorings through Cross-Coupling
Song, Jianxin,Kim, Pyosang,Aratani, Naoki,Kim, Dongho,Shinokubo, Hiroshi,Osuka, Atsuhiro WILEY-VCH Verlag 2010 Chemistry Vol.16 No.10
<B>Graphic Abstract</B> <P>The bridge determines the size of the loop? Palladium-catalyzed cross-coupling of borylporphyrins led to the construction of β-pyridine-bridged porphyrin nanorings in good yields (around 55–60 %; see scheme). The photophysical study revealed that these nanorings exhibit weakly coupled chromophores and longer fluorescent lifetimes, which is an apparent advantage in the process of efficient excited energy transfer. <img src='wiley_img_2010/09476539-2010-16-10-CHEM200903177-content.gif' alt='wiley_img_2010/09476539-2010-16-10-CHEM200903177-content'> </P>
Directly Pd(II)-Bridged Porphyrin Belts with Remarkable Curvatures
Song, Jianxin,Aratani, Naoki,Heo, Ji Haeng,Kim, Dongho,Shinokubo, Hiroshi,Osuka, Atsuhiro American Chemical Society 2010 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.132 No.34
<P>A β,β′-doubly 2,6-pyridylene-bridged porphyrin dimer and trimer were prepared by Suzuki−Miyaura coupling reactions and confirmed to have largely bent structures. These oligoporphyrins were readily metalated via <I>meso</I>-C−H bond activation with the assistance of the pyridyl nitrogen atoms to produce the corresponding Pd(II) complexes, which display even larger bent structures and larger TPA values at 800 nm.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2010/jacsat.2010.132.issue-34/ja1046654/production/images/medium/ja-2010-046654_0004.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja1046654'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja1046654'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja1046654'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja1046654'>ACS Electronic Supporting Info</A></P>
Yamaguchi, Ryuichi,Ito, Satoru,Lee, Byung Sun,Hiroto, Satoru,Kim, Dongho,Shinokubo, Hiroshi Wiley (John WileySons) 2013 Chemistry, an Asian journal Vol.8 No.1
<P>We have demonstrated that the iridium-catalyzed direct borylation of hexa-peri-hexabenzocoronene (HBC) enables regioselective introduction of boryl groups to the para-, ortho-, and meta-substituted HBCs in high yields. The boryl groups have been transformed into various functionalities such as hydroxy, cyano, ethynyl, and amino groups. We have elucidated that the substituents significantly influence the photophysical properties of HBCs to enhance fluorescence quantum yields. DFT calculations revealed that the origin of the substituent effect is the lift in degeneracy in the frontier orbitals by an interaction with electron-donating and electron-withdrawing substituents at the para- and ortho-positions. The change in molecular orbitals results in an increase of the transition probability from the S(0)S(1) states. In addition, the two-photon absorption cross-section values of para-substituted HBCs are significantly larger than those of ortho- and meta-substituted HBCs.</P>
Synthesis of Directly Connected BODIPY Oligomers through Suzuki–Miyaura Coupling
Hayashi, Yosuke,Yamaguchi, Shigeru,Cha, Won Young,Kim, Dongho,Shinokubo, Hiroshi American Chemical Society 2011 ORGANIC LETTERS Vol.13 No.12
<P>Treatment of a <I>meso</I>-arylboron dipyrrin (BODIPY) with NBS provides mono- and dibrominated BODIPYs at the 2- and 6-positions in excellent yields with high regioselectivity. Brominated products can be employed as a nice building block for the synthesis of a variety of BODIPY derivatives through Suzuki–Miyaura coupling. Because of a lack of substituents at the 1,3,5,7-positions, a directly β–β-linked BODIPY dimer exhibits a completely coplanar conformation of BODIPY units, offering effective π-conjugation.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/orlef7/2011/orlef7.2011.13.issue-12/ol200799u/production/images/medium/ol-2011-00799u_0001.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ol200799u'>ACS Electronic Supporting Info</A></P>