Metalloporphyrins, applications

Binding of organic nitroso compounds to metalloporphyrins 99ACR529. Design and applications of chiral porphyrins 98YGK201. 

Bis(cyclopentadienyl) complexes are central to the organometallic chemistry of the early transition metals and feature in applications such as alkene polymerization chemistry. Parallels can be drawn between a porphyrin ligand and two cyclopentadienyl ligands, in that they both contribute a 2— formal charge and exert a considerable steric influence on other ligands in the same molecule. Several of the metalloporphyrin complexes discussed below have bis(cyclopentadienyl) counterparts, and authors in some ca.ses have drawn quite detailed comparisons, although these discussions will not be repeated here. 

D. Applications of Metalloporphyrins as Multimodal, Optical, and/or Radioactive Imaging Probes... 

Verrelli, G., Lvova, L., Paolesse, R., Di Natale, C., and D Amico, A. (2007). Metalloporphyrin-based Electronic Tongue An application for the analysis of Italian white wines. Sensors 7 (11), 2750-2762. 

Porphyrin-based self-assembled molecular squares 389 can form mesoporous thin films in which the edge of a square, thus the size of the cavity, can be adjusted by appropriate choice of substituents [8]. Fibers that form coil-coiled aggregates with distinct, tunable helicity are built from crown ethers bearing porphyrins 390 [9]. In addition to the porphyrin applications discussed in Sections 6.3.2.2 and 6.4, dendrimer metalloporphyrins 391 to be applied in catalysis [10] and the water-soluble dendritic iron porphyrin 319 modelling globular heme proteins [11] can be mentioned. 

A decade ago, almost every metal had been inserted into a porphyrin, i.e., the periodic table of metalloporphyrins was nearly completed [8, 29], A review article devoted to the porphyrin complexes of individual metals gave examples for metal insertions according to following reactions (1) to (8) [8] for abbreviations see Table 1. Recent applications and improvements are noted below the respective equations. 

The first synthetic method which involves the preformed corrole ring is the application to corroles of Adler s synthesis of metalloporphyrinates [20],... 

Metal nanoparticles have extraordinary size-dependent optical properties, not present in the bulk metal and have, consequently, been the subject of intense research during the past decade or so.27 Attention has recently focused on functionalising colloidal nanoparticles with molecular recognition components for potential sensing applications.28,29,30 We have prepared a new amido-disulfide functionalised zinc metalloporphyrin (8) which was self-assembled on to gold nanoparticles to produce a novel anion-selective optical sensing system (9) (Scheme 3).4... 

The second example of the application of TDDFT to the electronic spectroscopy of metalloporphyrins concerns a CO-ligated iron porphyrin, a system that models the active centers of hemoproteins, recently investigated by Head-Gordon et al [146, 147] in the context of a theoretical study of the initial step of the photodissociation pathway of CO-ligated heme. 

As shown in Fig. 1-33, metalloporphyrins exhibit a number of porphyrin core vibrations in which local modes such as v(C=C) and v(C=N) are strongly coupled (Section 1.21) due to its planar 7r-conjugated structure. Several groups of workers (5-8) have carried out normal coordinate analysis on metalloporphyrins. If we consider the simplest metalloporphyrin in which all the peripheral groups are the hydrogen atoms, it should have 105 (3 x 37 - 6) normal vibrations, which can be classified under D4h symmetry as shown in Table 4-4. Table 4-5 shows major local coordinates that describe general characters of 35 Raman-active in-plane vibrations (8) together with observed frequencies for Ni(OEP) (Fig. 1-32). These normal mode descriptions are applicable to other metalloporphyrins with minor modifications. 

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