VU Research Portal Phosphole and Phosphine Acetylene Building Blocks for n-Conjugated Systems Weymiens, W. 2012 document version Publisher's PDF, also known as Version of record Link to publication in VU Research Portal citation for published version (APA) Weymiens, W. (2012). Phosphole and Phosphine Acetylene Building Blocks for n-Conjugated Systems. General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. E-mail address: [email protected] Download date: 25. Sep. 2021 Phospholes and Phosphine-Acetylenes: Overview of this Thesis |1 8 Chapter 1: Overview 1| Phospholes and Phosphine-Acetylenes: Overview of this Thesis 1.1. Introduction Being neglected for several decades, phosphorus is now being introduced in π-conjugated molecular frameworks with great success. Research in this respect has mainly focused on the phosphole ring, but other phosphorus-containing unsaturated moieties, such as the phosphine-acetylene unit, are also employed. This thesis is dedicated to the synthesis and spectroscopic and computational analysis of novel phosphorus-containing π-systems, based on the phosphole (structure on the left) and the phosphine-acetylene (structure on the right) building blocks. 1.2. Overview of this thesis This thesis commences with two literature chapters. Chapter 2 gives an overview of the most important developments and the current status of phosphole-containing π-conjugated materials. Chapter 3 provides a literature review on macrocycles and cages containing the phosphine-acetylene building block, with great emphasis on the π-conjugated ones. Chapter 4 contains the contribution to the field of 2,5-bisaryl-phosphole based π-systems. Herein, the introduction of azide moieties in these systems is described, which provides a handle for easy extension of the π-conjugated framework and as such fine-tuning of the photophysical properties thereof. The subject of chapter 5 is related to the field of fused phosphole-containing ring systems, in which an elegant synthetic route towards asymmetrically bridged trans- stilbenes is described, containing both a sulphur and a phosphorus atom. Moreover, differently sized substituents on phosphorus are used to influence the photophysical properties by tuning the participation of the phosphorus lone pair in the π-system. In chapter 6, the attention shifts towards the phosphine-acetylene building block. This chapter describes the synthetic attempts towards asymmetric macrocycles, in which two 1,2-bisethynylbenzene moieties are bridged by phosphorus and a different heteroatom. .