共查询到20条相似文献,搜索用时 11 毫秒
1.
Hirotaka Mori Taeyeon Kim Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka 《化学:亚洲杂志》2016,11(9):1454-1463
New hybrid porphyrin tapes comprising meso‐3,5‐di‐tert‐butylphenyl‐substituted ZnII‐porphyrins ( D ) and meso‐pentafluorophenyl‐substituted ZnII‐porphyrins ( A ) were synthesized via cross‐condensation of meso‐formyl porphyrins 1 , 5 , and 9 with oligopyrromethanes 2 and 6 as key steps. These hybrid tapes exhibit improved solubilities and enhanced chemical stability as compared with original Dn porphyrin tapes, and all display remarkably coplanar structures favorable for π‐conjugation. The absorption spectrum of ADDA displays Q‐like bands at 1400 and 1657 nm with a vibronic structure characteristic of porphyrinoids. The cyclic voltammograms exhibited positively shifted oxidation and reduction waves in the order of DDD < DAD < ADA < AAA . Tetrameric tape ADDA displays five reversible waves in a narrow range of 1.13 V. Two‐photon absorption (TPA) measurement confirmed that the π‐conjugation path is extended from 12 to ADDA and the molecular polarizability of ADA is larger than that of AAA . 相似文献
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Prof. Yasuhiro Morisaki Shizue Ueno Prof. Akinori Saeki Atsushi Asano Prof. Shu Seki Prof. Yoshiki Chujo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(14):4216-4224
[2.2]Paracyclophane‐based through‐space conjugated oligomers and polymers were prepared, in which poly(p‐arylene–ethynylene) (PAE) units were partially π‐stacked and layered, and their properties in the ground state and excited state were investigated in detail. Electronic interactions among PAE units were effective through at least ten units in the ground state. Photoexcited energy transfer occurred from the stacked PAE units to the end‐capping PAE moieties. The electrical conductivity of the polymers was estimated using the flash‐photolysis time‐resolved microwave conductivity (FP‐TRMC) method and investigated together with time‐dependent density functional theory (TD‐DFT) calculations, showing that intramolecular charge carrier mobility through the stacked PAE units was a few tens of percentage larger than through the twisted PAE units. 相似文献
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Guangxian Su Qizhao Li Masatoshi Ishida Chengjie Li Feng Sha Xin‐Yan Wu Lu Wang Glib Baryshnikov Dawei Li Hans gren Hiroyuki Furuta Yongshu Xie 《Angewandte Chemie (International ed. in English)》2020,59(4):1537-1541
An N‐confused phlorin isomer bearing a dipyrrin moiety at the α‐position of the confused pyrrole ring ( 1 ) was synthesized. PdII and BIII coordination at the peripheral prodigiosin‐like moiety of 1 afforded the corresponding complexes 2 and 3 . Reflux of 2 in triethylamine (TEA) converted the meso‐phenyl into the PdII‐coordinating phenoxy group to afford 4 . Under the same reaction conditions, TEA was linked to the α‐position of the dipyrrin unit in 3 as an N,N‐diethylaminovinyl group to afford 5 . Furthermore, peripheral coordination of BIII in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of AgIII at the inner cavity to afford 3‐Ag and 5‐Ag , respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination. 相似文献
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Yutao Rao Taeyeon Kim Kyu Hyung Park Fulei Peng Lei Liu Yunmei Liu Bin Wen Prof. Dr. Shubin Liu Prof. Dr. Steven Robert Kirk Licheng Wu Prof. Dr. Bo Chen Prof. Dr. Ming Ma Dr. Mingbo Zhou Dr. Bangshao Yin Dr. Yuexing Zhang Prof. Dr. Dongho Kim Prof. Dr. Jianxin Song 《Angewandte Chemie (International ed. in English)》2016,55(22):6438-6442
β,β‐tripyrrin‐bridged earring porphyrins were synthesized through Suzuki–Miyaura cross coupling reactions. These porphyrinoids have multiple cavities and can accommodate two or three metal ions per molecule. The structures of the porphyrins have been elucidated by x‐ray diffraction analysis, and feature curved π planes. The electronic spectra of the porphyrins exhibit near‐infrared (NIR) absorptions and metal insertion leads to red‐shifted and intensified absorption features. Electrochemical analysis and transient absorption measurements indicated that the porphyrins exhibit effective electronic communication between their central and peripheral moieties. 相似文献
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Prof. Dr. Tetsuo Okujima Tasuku Kikkawa Prof. Dr. Haruyuki Nakano Hiroshi Kubota Nobumasa Fukugami Prof. Dr. Noboru Ono Prof. Dr. Hiroko Yamada Prof. Dr. Hidemitsu Uno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12854-12863
Bicyclo[2.2.2]octadiene (BCOD) fused azuliporphyrins were synthesized by 3+1 porphyrin synthesis of azulitripyrranes with diformylpyrroles. Subsequent retro‐Diels–Alder reaction of the BCOD‐fused azuliporphyrins afforded azulibenzo‐, azulidibenzo‐, and azulitribenzoporphyrins 1 – 5 . NMR and UV/Vis spectra, as well as nucleus‐independent chemical shift (NICS) calculations revealed that 1 – 5 and their diprotonated dications exhibit relatively low porphyrinoid aromaticity, which was dependent on the position and number of fused benzene rings present. 相似文献
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β‐Octamethoxy‐Substituted 22π and 26π Stretched Porphycenes: Synthesis,Characterization, Photodynamics,and Nonlinear Optical Studies 下载免费PDF全文
Anup Rana Sangsu Lee Prof. Dr. Dongho Kim Dr. Pradeepta K. Panda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(34):12129-12135
Three meso‐expanded tetrapyrrolic aromatic macrocycles, including 22π and 26π acetylene–cumulene bridged stretched octamethoxyporphycenes and octamethoxy[22]porphyrin‐(2.2.2.2), are reported, for the first time, by modification of previously reported synthetic methods. This strategy led to an enhancement in the overall yield of their corresponding octaethyl analogues. The methoxy‐substituted expanded porphycenes display slightly blueshifted absorption relative to their ethyl analogues, along with very weak fluorescence, probably due to efficient intramolecular charge transfer (ICT). Additionally, the two‐photon absorption (TPA) cross sections of these macrocycles were evaluated; these are strongly related to core expansion of the porphyrin aromaticity through increased meso‐bridging carbon atoms as well as conformational flexibility and substitution effects at the macrocyclic periphery. In particular, the octamethoxy stretched porphycenes display strong TPA compared with the octaethyl analogues due to the dominant ICT character of methoxy groups with a maximum TPA cross section of 830 GM at 1700 nm observed for 26π‐octamethoxyacetylene–cumuleneporphycene. 相似文献
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Qingshan Hao Dr. Yi Zeng Dr. Tianjun Yu Dr. Jinping Chen Prof. Dr. Guoqiang Yang Prof. Dr. Yi Li 《化学:亚洲杂志》2013,8(5):1015-1022
A series of doubly β‐to‐β bridged cyclic ZnII porphyrin arrays were prepared by a stepwise Suzuki–Miyaura coupling reaction of borylated ZnII porphyrin with different bridge groups. The coupling of the building block of β,β′‐diboryl ZnII porphyrin 1 with different bridges provided the doubly β‐to‐β carbazole‐bridged ZnII porphyrin array 3 , the fluorene‐bridged ZnII porphyrin array 5 , the fluorenone‐bridged ZnII porphyrin array 7 , and the three‐carbazole‐bridged ZnII porphyrin ring 8 . The structural assignment of 3 was confirmed by the X‐ray diffraction analysis, which revealed a highly symmetrical and remarkably bent syn‐form structure. The incorporation of bridge units with different electronic effects results in different photophysical properties of the cyclic ZnII porphyrin arrays. Comprehensive photophysical studies demonstrate that the electron‐withdrawing bridge fluorenone has the largest electronic interaction with the ZnII porphyrin unit among the series, thus resulting in the highest two‐photon absorption cross‐section values (σ(2)) of 6570±60 GM for 7 . The present work provides a new strategy for developing porphyrin‐based optical materials. 相似文献
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Dr. Hua‐Wei Jiang Taeyeon Kim Dr. Takayuki Tanaka Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):83-87
Directly 2,12‐ and 2,8‐linked ZnII porphyrin oligomers were prepared from 2,12‐ and 2,8‐diborylated ZnII porphyrin by a cross platinum‐induced coupling with a 2‐borylated ZnII porphyrin end unit followed by a triphenylphosphine (PPh3)‐mediated reductive elimination. Comparative studies on the steady‐state absorption and fluorescence spectra and the fluorescence lifetimes led to a conclusion that the exciton in the S1 state is delocalized over approximately four and two ZnII porphyrin units for 2,12‐ and 2,8‐linked ZnII porphyrin arrays, respectively. 相似文献
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Recent progress in the synthesis of covalently linked porphyrin arrays with large two‐Photon absorption (TPA) cross‐section values has been reviewed with a particular focus on the relation of TPA properties with molecular structures. Covalently linked porphyrin arrays continue to be important and useful for the creation of functional materials owing to their chemical robustness, fine‐tuning, and easy manipulation. More importantly, the porphyrin electronic systems are quite susceptible to periphery conjugative perturbations, hence allowing facile fabrications to extensively delocalized systems. This property has been used for exploration of porphyrin‐based molecular systems with large TPA values, demonstrating a general trend that enhancement in electronic interactions leads to large TPA cross‐section values. As a representative example, the porphyrin tapes exhibit larger TPA values owing to the fully delocalized nature of the π‐electrons. This Focus Review will help understand the structural requirements of porphyrin arrays with large TPA values, which will be useful for future applications in optical communication in the IR region. 相似文献
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Dr. M. Rajeswara Rao Antonin Desmecht Prof. Dmitrii F. Perepichka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6193-6201
A series of π‐extended aromatic indenofluorene (IF) analogues with naphthalene and anthracene cores have been synthesized through acid‐catalyzed intramolecular cyclization. The regioselectivity of the reaction is controlled by a combination of steric and electronic factors and in some cases several possible regioisomers have resulted from the same precursor. The effects of ring connectivity on the optoelectronic properties were investigated by DFT calculations, absorption/emission spectroscopy, cyclic voltammetry, and spectroelectrochemical studies. All regioisomers exhibited a redshift of their absorption/emission bands relative to the parent IF analogues, but the magnitude of this shift and other optoelectronic properties (luminescence quantum yield, etc.) depends on the ring connectivity in a less obvious manner. 相似文献
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Chihiro Maeda Pyosang Kim Sung Cho Jong Kang Park Jong Min Lim Dongho Kim Prof. Dr. Josh Vura‐Weis Michael R. Wasielewski Prof. Dr. Hiroshi Shinokubo Prof. Dr. Atsuhiro Osuka Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(17):5052-5061
meso‐Triazolyl‐appended ZnII–porphyrins were readily prepared by CuI‐catalyzed 1,3‐dipolar cycloaddition of benzyl azide to meso‐ethynylated ZnII–porphyrin (click chemistry). In noncoordinating CHCl3 solvent, spontaneous assembly occurred to form tetrameric array ( 3 )2 from meso–meso‐linked diporphyrins 3 , and dodecameric porphyrin squares ( 4 )4 and ( 5 )4 from the L ‐shaped meso–meso‐linked triporphyrins 4 and 5 . The structures of these assemblies were examined by 1H NMR spectra, absorption spectra, and their gel permeation chromatography (GPC) retention time. Furthermore, the structures of the dodecameric porphyrin squares ( 4 )4 and ( 5 )4 were probed by small‐ and wide‐angle X‐ray scattering (SAXS/WAXS) measurements in solution using a synchrotron source. Excitation‐energy migration processes in these assemblies were also investigated in detail by using both steady‐state and time‐resolved spectroscopic methods, which revealed efficient excited‐energy transfer (EET) between the meso–meso‐linked ZnII–porphyrin units that occurred with time constants of 1.5 ps?1 for ( 3 )2 and 8.8 ps?1 for ( 5 )4. 相似文献
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Synthesis of 7,8‐Dehydropurpurin Dimers and Their Conversion into Conformationally Constrained β‐to‐β Vinylene‐Bridged Porphyrin Dimers 下载免费PDF全文
Norihito Fukui Prof. Dr. Hideki Yorimitsu Dr. Jong Min Lim Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka 《Angewandte Chemie (International ed. in English)》2014,53(17):4395-4398
7,8‐Dehydropurpurin has attracted much attention owing to the dual 18π‐ and 20π‐electron circuits in its macrocyclic conjugation. The two‐fold Pd‐catalyzed [3+2] annulation of meso‐bromoporphyrin with 1,4‐diphenylbutadiyne furnished 7,8‐dehydropurpurin dimers. The 8a,8a‐linked dimer displays a red‐shifted and enhanced absorption band in the NIR region and a small electrochemical HOMO–LUMO band gap as a consequence of efficient conjugation between the two coplanar 7,8‐dehydropurpurin units. Treatment of this dimer with N‐bromosuccinimide in chloroform and ethanol gave β‐to‐β vinylene‐bridged porphyrin dimers. Owing to the highly constrained conformations, these dimers exhibit perturbed absorption spectra, small Stokes shifts, and high fluorescence quantum yields. 相似文献
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Dr. Oliver Locos Dr. Bruno Bašić Dr. John C. McMurtrie Dr. Paul Jensen Prof. Dennis P. Arnold 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(18):5574-5588
Homo‐ and heteronuclear meso,meso‐(E)‐ethene‐1,2‐diyl‐linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15‐triphenylporphyrin (TriPP) on both ends of the ethene‐1,2‐diyl bridge M210 (M2=H2/Ni, Ni2, Ni/Zn, H4, H2Zn, Zn2) and 5,15‐bis(3,5‐di‐tert‐butylphenyl)porphyrinato‐nickel(II) on one end and H2, Ni, and ZnTriPP on the other ( M211 ), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni2 bis(TriPP) complex Ni210 , single crystal X‐ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of NiII porphyrins, and the (E)‐C2H2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H410 and H2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas‐phase optimized geometry of Ni210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. 相似文献
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Inside Cover: π‐Extended “Earring” Porphyrins with Multiple Cavities and Near‐Infrared Absorption (Angew. Chem. Int. Ed. 22/2016) 下载免费PDF全文
Yutao Rao Taeyeon Kim Kyu Hyung Park Fulei Peng Lei Liu Yunmei Liu Bin Wen Prof. Dr. Shubin Liu Prof. Dr. Steven Robert Kirk Licheng Wu Prof. Dr. Bo Chen Prof. Dr. Ming Ma Dr. Mingbo Zhou Dr. Bangshao Yin Dr. Yuexing Zhang Prof. Dr. Dongho Kim Prof. Dr. Jianxin Song 《Angewandte Chemie (International ed. in English)》2016,55(22):6346-6346
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Frontispiece: Supramolecular Interaction of Fullerenes with a Curved π‐Surface of a Monomeric Quadruply Ring‐Fused Porphyrin 下载免费PDF全文
Yuta Saegusa Dr. Tomoya Ishizuka Dr. Tatsuhiro Kojima Dr. Shigeki Mori Prof. Dr. Masaki Kawano Prof. Dr. Takahiko Kojima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14)