FU Berlin Digitale Dissertation
Christian Grave : A Set of Shape-Persistent Macrocycles with Terpyridine Units Ein Satz formtreuer Makrozyklen mit Terpyridineinheiten
|Abstract| |Table of Contents| |More Information|

Abstract This work describes the synthesis of shape-persistent phenylacetylene macrocycles with 2,2':6',2''-terpyridine units. These compounds are principally suitable for forming columnar structures by self-aggregation as well as for binding metal ions in their interior. They are therefore of considerable interest as building blocks for supramolecular arrays. The ring precursor units were made accessible by different palladium catalyzed C-C coupling reactions (Sonogashira, Stille, Suzuki). A set of 10 macrocycles with 46, 50 or 58 ring members, one or two terpyridine units and different substitution patterns were gained by Sonogashira or Glaser coupling of two half-ring precursors. For three 46-membered cycles, the structure in the solid state could be analyzed by X-ray crystallography on single crystals. The cycles have inner diameters of 1.2 x 1.9 nm and form layered structures. For a 46-membered cycle, the 2-D structure of a monolayer on graphite could be examined by scanning tunneling microscopy. Initial experiments to form complexes of the terpyridine compounds with Cu2+ or Ru2+ were performed.

Table of Contents Download the whole PhDthesis as a zip-tar file or as zip-File For download in PDF format click the chapter title TITLE AND CONTENTS Acknowledgement Abbreviations 1. INTRODUCTION 1 2. AIM OF THE WORK 3 3. LITERATURE SURVEY 4 3.1 Synthetic Strategies 4 3.2 Shape-persistent macrocycles with heteroatoms 8 4. GENERAL PART 15 4.1 General Strategy 15 4.2 Synthesis of the building blocks 21 4.3 Synthesis of the 46-membered cycles 35 4.4 Synthesis of the 58-membered cycles 52 4.5 A 50-membered cycle with two terpyridine units 61 4.6 Characterization and properties of the cycles 64 4.7 Outlook: Metal Complexes 91 5. SUMMARY 97 6. ZUSAMMENFASSUNG 99 7. EXPERIMENTAL PART 101 7.1 General 101 7.2 Syntheses 103 7.2.1 Compounds of Chapter 4.3 103 7.2.2 Compounds of Chapter 4.4 120 7.2.3 Compounds of Chapter 4.5 160 7.2.4 Compounds of Chapter 4.6 and 4.8 173 7.3 Crystallographic data 177 REFERENCES AND REMARKS 178

More Information:
Online available:	http://www.diss.fu-berlin.de/2002/156/indexe.html
Language of PhDThesis:	english
Keywords:	Synthesis, Macrocycles, Terpyridines, Shape persistency, Cross-coupling
DNB-Sachgruppe:	30 Chemie
Date of disputation:	26-Jul-2002
PhDThesis from:	Fachbereich Biologie, Chemie, Pharmazie, Freie Universität Berlin
First Referee:	Prof. Dr. Arnulf Dieter Schlüter
Second Referee:	Prof. Dr. Jürgen-H. Fuhrhop
Contact (Author):	grave@chemie.fu-berlin.de
Contact (Advisor):	adschlue@chemie.fu-berlin.de
Date created:	15-Aug-2002
Date available:	21-Aug-2002

 

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