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The porphyrin handbook - Kadish K.M.

Kadish K.M. The porphyrin handbook - Academic press, 2000. - 368 p.
Download (direct link): kadishsmishgulilard2000.djvu
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............................. 72
1. Porous Molecular Porphyrin
Structures...............................................................
.............. 73
2. Hydrogen-Bonded Network
Materials................................................................
................. 77
3. Metal-lon Coordination Network
Materials................................................................
.......... 85
4. Porphyrin-Incorporated
Zeolites.................................................................
.................. 87
5. Clays and Layered Materials Incorporating
Porphyrins..............................................................
94
B. Conductive Polymers and
Ferroelectrics...........................................................
................. 102
1. Conductive Porphyrin
Polymers.................................................................
.................... 102
2. Ferroelectric Porphyrin
Materials................................................................
................. Ill
C. Porphyrin-Based Chemical
Sensors..................................................................
................ 114
1. Gas
Sensors..................................................................
..................................... 114
2. Sensors for Solution
Species..................................................................
.................... 120
IV.
Conclusions..............................................................
.............................................. 127

References...............................................................
............................................... 128
The Porphyrin Handbook
K.M. Kadish, K.M. Smith, R. Guilard, Eds.
Volume 6 / Applications: Past, Present and Future

Copyright 2000 by Academic Piess All rights ol reproduction in any form
reserved, ISBN 0-12-393200-9/S30 00
44
Chou et al.
I.
Introduction
Porphyrins and related macrocycles provide an extremely versatile
synthetic base for a variety of materials applications. The exploration
of metalloporphyrin assemblies as building blocks for tailored materials
properties has grown rapidly during the past decade.1 In this chapter, we
shall review the rather diverse applications of porphyrins to materials
chemistry and try to draw the common threads between these topics.
Porphyrins and metalloporphyrins have broad applications as field-
responsive materials, particularly for optoelectronic applications. For
example, the facile substitution of the periphery of various porphyrins
has generated a series of unusual liquid crystalline materials. The
porphyrin ligand serves as a platform on which one can erect desirable
molecular and materials properties, including very large dipole moments,
polarizabilities, and hyperpolarizabilities. The nonlinear optical
properties of these materials are of special interest, in part for energy
transfer with molecular control, and in part for potential applications
in optical communications, data storage, and electrooptical signal
processing. The stability of mono- and di-cation porphyrin 7r-radicals
makes these systems especially interesting for photoionization processes,
closely related to the so-called special-pair reaction center of
photosynthesis and the photogeneration of electron transfer. Also,
various polymeric porphyrins have been examined for their unusual
lowdimensional conductivity.
In contrast to their interaction with applied electric, magnetic or
electromagnetic fields, porphyrins and metalloporphyrins can also
interact with other chemical species. One might view such interactions as
chemo-responsive rather than field-responsive. The development of chemo-
responsive materials based on porphyrins, however, is somewhat less
advanced. One example of such applications is that porphyrin solids,
being highly porous, are involved in the current development of
molecularly based molecular sieves or shape-selective solid catalysts.
Porphyrins and metalloporphyrins have also been examined for a variety of
sensor applications, further proving their importance as a class of
chemo-responsive materials.
II. Photonic Materials
A. MESOGENIC PORPHYRINS
Appending long alkyl chains to the periphery of a rigid tetrapyrrolic
core has proved to be a general methodology for the synthesis of liquid
crystalline materials. Liquid crystals possess properties of both the
liquid and solid phases, possessing order over intermediate distances,
but retaining many of the rheological properties of liquids.
Phthalocyanine derivatives have been widely investigated as thermotropic
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