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Photoactive heavy transition metal conjugates

English title Photoactive heavy transition metal conjugates
Applicant Housecroft Catherine Elizabeth
Number 126465
Funding scheme Project funding (Div. I-III)
Research institution Institut für Anorganische Chemie Universität Basel
Institution of higher education University of Basel - BS
Main discipline Inorganic Chemistry
Start/End 01.10.2009 - 30.09.2011
Approved amount 125'056.00
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Keywords (10)

gold; coordination; photoemissive; photoactive; luminescence; devices; LECs; emissive; alkyne; heterocyclic compounds

Lay Summary (English)

Lead
Lay summary
The 2-year project focuses on the syntheses, solid-state structures, and solid-state and solution emissive properties of gold(I)-containing compounds containing heterocyclic (terpyridine, tpy, based) metal-bidning domains.We will synthesize 4'-alkynyl tpy derivatives in which the alkyne and tpy domains are directly attached. The incorporation of the gold-alkyne units renders the compounds luminescent. Structure-property relationships in regard of turning on/offinteractions between the gold atoms, and the emissive behaviour of the new compounds will be assessed. Multitopic tpy-containing building blocks will be combined with the new ligands to assemble gold-terminated, linear or planar arrays. We will use bridging phosphine ligands in order to access coordination polymers and 2D or 3D networks. The main aim of the project is to gain control over the emissive behaviour of the compounds by making moderately small changes to the structures of the compounds. Both solution and solid state behaviour will be studied.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Photoactive building blocks for coordination complexes: Gilding 2,2′:6′,2″-terpyridine
Constable EC, Housecroft CE, Kocik MK, Zampese JA (2011), Photoactive building blocks for coordination complexes: Gilding 2,2′:6′,2″-terpyridine, in Polyhedron, 30(16), 2704-2710.

Associated projects

Number Title Start Funding scheme
117627 Assembly of nanometric photonicmolecular devices 01.10.2007 Project funding (Div. I-III)
133766 Mechanistic and structural investigations by NMR spectroscopy on a wide scope of compounds - from natural products and proteins to artificial enzymes, organometal catalysts and supramolecular materials 01.12.2010 R'EQUIP

Abstract

Two related projects are proposed. Sub-project A represents a continuation of project 200021-117627 and will support years 3 and 4 of Ph.D. student Marzena Kocik. Both sub-projects exploit the luminescent properties of d(10)-containing molecular architectures which are assembled using reactions of 2,2':6',2"-terpyridine (tpy) or 2,2'-bipyridine (bpy) ligands bearing peripheral units containing mono- or di- gold(I) or copper(I) derivatives. Sub-project A focuses on the syntheses, solid-state structures, and solid-state and solution emissive properties of gold(I)-containing tpy ligands and their metal complexes. We will synthesize 4'-alkynyl tpy derivatives in which the alkyne and tpy domains are directly attached. Standard conditions will be used to couple the terminal alkyne to a gold(I) phosphine unit (mono- or dinuclear), and a systematic study of the solid-state structural properties as a function of the steric demands of the PR3 group will be carried out. Structure-property relationships in regard of turning on/off aurophilic interactions and emissive behaviour will be assessed. Multitopic tpy-containing building blocks will be combined with the new ligands to assemble gold-terminated, linear or planar arrays, or coordination polymers and networks if bridging phosphine ligands are incorporated. Finally, by using pyPh2PAuCl (py = pyridyl substituent), 4'-(pyPh2PAuC=C)tpy will be prepared and its coordination properties (tpy and py domains) investigated, with the main of forming coordination polymers containing gold(I) centres in their backbone. The focus of Sub-project B will be to utilize the emissive properties of gold(I) compounds already in house, and related derivatives in the preparation of novel conjugate materials for incorporation in light emitting electrochemical cells (LECs). The project will use 2,2'-bipyridine (bpy) based ligands, terminated in gold(I) or copper(I) phosphine units incorporated into iridium(III) complexes. The key characteristics of these target complexes are: (i) luminescent gold(I) and copper(I) centres, (ii) luminescent iridium(III) centres, and (iii) intramolecular pi-stacking to give long-lived LECs. Of prime importance for this project is device fabrication and testing which will be achieved through our (CEH and ECC) established collaboration with the University of Valencia.
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