Supramolecular Structure, Physical Properties, and Langmuir‐Blodgett Film Formation of an Optically Active Liquid‐Crystalline Phthalocyanine

Chemistry - A European Journal - Tập 1 Số 3 - Trang 171-182 - 1995
Cornelus F. van Nostrum1, Anton W. Bosman1, Gerwin H. Gelinck1, Pieter G. Schouten2, John M. Warman2, Arno P. M. Kentgens3, Marinus A. C. Devillers4, Andries Meijerink5, Stephen J. Picken6, Ulrich Sohling7, A. Schouten7, Roeland J. M. Nolte1
1Department of Organic Chemistry, NSR Center University of Nijmegen, 6525 ED Nijmegen (The Netherlands), Telefax: Int. code + (80)553-450
2IRI, Delft University of Technology, (The Netherlands)
3SON/NWO HF NMR Facility, University of Nijmegen, (The Netherlands)
4Experimental Solid State Physics, University of Nijmegen, (The Netherlands)
5Physics Laboratory, University of Utrecht, The Netherlands
6Akzo Nobel Central Research, Physical Chemistry Department, Arnhem, (The Netherlands)
7Laboratory of Polymer Science, University of Groningen, (The Netherlands)

Tóm tắt

AbstractThe structure and physical properties of optically active, metal‐free 2,3,9,10,16,17,23,24‐octa (S‐3,7‐dimethyloctoxy)phthalocyanine ((S)‐Pc(8,2)) are reported and compared with those of the phthalocyanine with (R,S) side chains (mixture of 43 stereoisomers). Unlike the latter compound, (S)‐Pc(8,2) lacks a crystalline phase. A freshly prepared sample is in a distorted mesophase and reorganizes irreversibly to a more ordered phase above 65 °C. X‐ray diffraction and circular dichroism studies indicate that the molecules are stacked in columns which have a hexagonal arrangement and a left‐handed helical superstructure, that is, a novel chiral Dh* mesophase. Solid state NMR measurements reveal that the phthalocyanine units in the columns begin to vibrate laterally when the temperature is increased. At 111 °C (Dh* → Dr transition) they start to rotate around their columnar axes and at the same time the side chains become liquidlike. Energy migration is very efficient in the chiral Dh* phase and also in the frozen mesophase below 3 °C, as follows from luminescence spectroscopy. Intracolumnar charge transport, studied by the time‐resolved microwave conductivity technique, turns out to be slower in the helically distorted columns than in linear columns. (S)‐Pc(8,2) forms a very stable bilayer at the air‐water interface, which can be transferred to give a high quality Langmuir‐Blodgett film. The fact that this phthalocyanine is mesogenic at room temperature is thought to be responsible for this behavior.

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Chemistry - A European Journal

Tập 1 Số 3

171-182

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