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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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Pingping Yao Yunfeng Qiu Dr. Penglei Chen Dr. Yanping Ma Dr. Shenggui He Prof. Dr. Jian‐Yu Zheng Prof. Dr. Minghua Liu Prof. Dr. 《Chemphyschem》2010,11(3):722-729
Molecular assemblies of metalloporphyrins trans‐dichloro(5,10,15,20‐tetra‐p‐tolylporphyrinato)tin(IV) (SnCl2TPPMe) and trans‐dihydroxo(5,10,15,20‐tetra‐p‐tolylporphyrinato)tin(IV) (Sn(OH)2TPPMe), which have two trans axial ligands, as well 5,10,15,20‐tetrakis(4‐methoxyphenyl)‐21H,23H‐porphine iron(III) chloride (FeClTPPOMe) and 5,10,15,20‐tetraphenyl‐21H,23H‐porphine manganese(III) chloride (MnClTPP), which have one axial ligand, are interfacially organized by Langmuir and Langmuir–Blodgett (LB) techniques. SnCl2TPPMe and Sn(OH)2TPPMe form nanofibrous structures which can display distinct supramolecular chirality, although the molecular units themselves are achiral, while FeClTPPOMe and MnClTPP form irregular nanoparticles that display negligible supramolecular chirality. An interpretation in terms of the effects of the axial ligands is proposed for this interesting phenomenon. Moreover, compared with assemblies of the diprotonated free‐base porphyrins, which are fabricated by interfacial (air/2.4 M HCl) organization of free‐base porphyrin, those of SnCl2TPPMe and Sn(OH)2TPPMe display higher stability in terms of supramolecular chirality. These results indicate that the assembly properties of metalloporphyrins can essentially be affected by the axial ligands that are attached to their chromophores, and that stable chiral porphyrin supramolecular associations can be easily produced by using achiral metalloporphyrins bearing two trans axial ligands. 相似文献
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