Multiporphyrin arrays

Fig. 3. A large multiporphyrin array arranged in a dendritic scaffold...

Gunter MJ (2006) Multiporphyrin Arrays Assembled Through Hydrogen Bonding 121 263-295... 

Fenyo, D. Chait, B. T. Johnson, T. Lindsey, J. S. Laser desorption mass spectrometry of synthetic multiporphyrin arrays. J. Porph. Phthalocyan. 1997, 1, 93-99. 

Wagner, R. W. Ciringh, Y. Clausen, C. Lindsey, J. S. Investigation and refinement of palladium-coupling conditions for the synthesis of diarylethyne-linked multiporphyrin arrays. Chem. Mater. 1999,11, 2974-2983. 

Wagner RW, Johnson TE, Lindsey JS (1996) J Am Chem Soc 118 11166-11180 Soluble synthetic multiporphyrin arrays. 1. Modular design and synthesis... 

Inorganic templating and self-assembly provide coordination compounds whose geometries make possible the synthesis of complex structures, namely of cyclic multiporphyrin arrays [9.13a, 9.179], of inorganic rotaxanes [9.97a, 9.180], of multi-catenates and catenands (see 181) [8.281, 8.282] and even of molecular knots (see 182) [8.282, 9.77, 9.181] (in 181 and 182 a) with, b) without Cu(l) template). 

Stang et al. [94JA4981, 9403776, 95JA1667, 95JA6273] described the self assembly of a series of unique cationic, tetranuclear, Pd(II)- and Pt(II)-based macrocyclic squares (e.g., 25), utilizing different bidentates as the sides of these structures. The similar self-assembly complexation of dipyridyl porphyrins by cis- and tran.v-substituted Pd(II) or Pt(II) ions possessing square planar coordination afforded multiporphyrin arrays with a square... 

Lammi RK, Ambroise A, Balasubramanian T, et al. Structural control of photoinduced energy transfer between adjacent and distant sites in multiporphyrin arrays. J Am Chem Soc 2000 122 7579-91. 

Choi M-S,YamazakiT,Yamazaki I, AidaT. Bioinspired molecular design of light-harvesting multiporphyrin arrays. Angew Chem Int Ed Eng 2004 43 150-8. 

Burrell AK, Officer DL, Plieger PG, Reid DCW. Synthetic routes to multiporphyrin arrays. Chem Rev 2001 101 2751-96. 

D. Holten, D.F. Bocian, J.S. Lindsey, Probing Electronic Communication in Covalently Linked Multiporphyrin Arrays. A Guide to the Rational Design of Molecular Photonic Devices , Acc. Chem. Res., 35,57 (2002)... 

Bioinspired molecular design of light-harvesting multiporphyrin arrays 04AG(E)150. 

Probing electronic communication in covalently linked multiporphyrin arrays 02ACR57. 

Scheme 21 Schematic of multiporphyrin array by Yamazaki and coworkers [70,71]...

Scheme 22 Multiporphyrin array connected by diphenylethynyl linkages by Lindsey and coworkers [72]...

FIGURE 5.16 Multiporphyrin array with suitable geometry for high energy transfer between the metallated donors and the free-base acceptors. 

Membrane-s )Anmn have been prepared. Tetraphenylpor-phyrins having jc-carboxy and jc-amino functionalities have been polymerized interfacially to produce chemically asymmetric membrane films.Mercaptoporphyrins have also been polymerized to form ultrathin films of a porphyrin homopolymer based upon 5,10,15,20-tetrakis-(Q -mercapto-j9-tolyl) porphyrin,and thiol-derivatized porphyrins for attachment to electroactive surfaces have been prepared and examined as means of information storage,including those having a ferrocenyl moiety appended in several ways. Various means of linking porphyrins to form arrays have been reviewed. Preparation and investigation of the physical properties of cyclic tetra-, hexa-, hepta-porphyrin and star-shaped multiporphyrin or star-shaped tetra- or octa-porphyrin, or monophthalocyanine arrays have been described and reviewed. As part of this work, methods of forming porphyrins in the presence of acid-labile metalloporphyrins that provide a new route to mixed-metal multiporphyrin arrays have been reported. ... 

Self-assembly principles of the formation of multiporphyrin arrays are extended to anchor the porphyrin triads on semiconductor CdSe/ZnS quantum dot (QD) surface. Comparing with individual counterparts (QD, pyridylsubstituted porphyrin H2P(p-Pyr)4, and Zn-octaethylporphyrin chemical dimer (ZnOEP Ph), the formation of heterocomposites QD-porphyrin triad results in the specific quenching of QD photoluminescence, accompanied by the dimer fluorescence strong quenching (Tsd 1-7 ps due to energy and/or electron transfer) and the noticeable decease of the extra-ligand H2P(p-Pyr)4 fluorescence efficiency by 1.5-2 times via hole transfer H2P—>dimer. 

Self-organization of multiporphyrin arrays into well-defined structmes, where two or more porphyrins are covalently linked together, form another set of supramolecular structures arranged through axial coordination. A combination of porphyrins with Ceo has been realized in several ways (Fig. 17). The Ceo unit forms a covalent bridge between two porphyrins, which are then oriented in a cofacial arrangement via DABCO-binding as in... 

In fact, hardly any donor atoms other than nitrogen have been used to create multiporphyrin assemblies. Using hard Lewis acids as central metal opens the possibility to bind two axial ligands on either side of the porphyrins. With ditopic Ugands such as diols this can lead to polymerization. However, a few examples can be found in the Uterature, where the central metal of the porphyrin is axially coordinated by oxygen, sulfur or selenium to assemble porphyrins. The use of (non-porphyrinic) phosphine ligands apparently has so far not been successful in the construction of supramolecular multiporphyrin arrays. 

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