edoc

Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6]

Nohara, Isaak and Prescimone, Alessandro and Housecroft, Catherine E. and Constable, Edwin C.. (2019) Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6]. Inorganics, 7 (11). pp. 1-15.

[img] PDF - Published Version
Available under License CC BY (Attribution).

2448Kb

Official URL: https://edoc.unibas.ch/69003/

Downloads: Statistics Overview

Abstract

We report the synthesis and characterization of [Cu(P^P)(N^S)][PF 6] complexes with P^P = bis(2-(diphenylphosphino)phenyl) ether (POP) or 4,5-bis(diphenylphosphino)-9,9- dimethylxanthene (xantphos) and N^S = 2-(iso-propylthio)pyridine (iPrSpy) or 2-(tert -butylthio)pyridine (tBuSpy). The single crystal structures of [Cu(POP)(iPrSPy)][PF 6] and [Cu(POP)(tBuSPy)][PF6] have been determined and confirm a distorted tetrahedral copper(I) centre and chelating P^P and N^S ligands in each complex. Variable temperature (VT) 1H and 31P{1H} NMR spectroscopy reveals dynamic behavior with motion of the POP backbone in [Cu(POP)(iPrSPy)][PF 6 ] and [Cu(POP)(tBuSPy)][PF6] frozen out at 238 K. VT NMR spectroscopic data including EXSY peaks in the ROESY spectrum of [Cu(xantphos)(tBuSPy)][PF6] at 198 K reveal that two conformers exist in an approximate ratio of 5:1. Replacing bpy by the N^S ligands shifts the Cu+/Cu2+ oxidation to a higher potential. The copper(I) compounds are weak emitters in the solid state with PLQY values of <2%. These values are similar to those for [Cu(POP)(bpy)][PF6] and [Cu(xantphos)(bpy)][PF6] in the solid state.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Nohara, Isaak and Prescimone, Alessandro
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:MDPI
e-ISSN:2304-6740
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:08 Mar 2019 14:04
Deposited On:26 Feb 2019 11:02

Repository Staff Only: item control page