Dataset : Unusual Triplet-Triplet Annihilation in a 3D Copper Chloride Coordination Polymer

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Adrien Schlachter ; Antoine Bonnot ; Daniel Fortin ; Paul-Ludovic Karsenti ; Michael Knorr ; Pierre D. Harvey (2019): Unusual Triplet-Triplet Annihilation in a 3D Copper Chloride Coordination Polymer. Royal Society of Chemistry. doi:10.25666/DATAOSU-2021-03-12-02

General metadata

Identifier : local : FR-18008901306731-2021-03-12-02 external : doi:10.25666/DATAOSU-2021-03-12-02, doi:10.1039/C9CP02891A
Description :
A new coordination polymer (CP) defined as [Cu2Cl2(EtS(CH2)4SEt)4]n (CP2) was prepared by reacting EtS(CH2)4SEt with CuCl in acetonitrile in a 1 : 2 stoichiometric ratio. The X-ray structure reveals formation of non-porous 3D material composed of parallel 2D-[Cu2Cl2S2]n layers of Cl-bridged Cu2(μ-Cl)2 rhomboids assembled by EtS(CH2)4SEt ligands. A weak triplet emission (Φe < 0.0001) is observed in the 400–500 nm range with τe of 0.93 (298 K) and 3.5 ns (77 K) as major components. CP2 is the only 2nd example of emissive thioether/CuCl-containing material and combined DFT/TDDFT computations suggest the presence of lowest energy M/XLCT excited states. Upon increasing the photon flux (i.e. laser power), a triplet–triplet annihilation (TTA) is induced with quenching time constants of 72 ps (kQ = 1.3 × 1010 s−1) and 1.0 ns (kQ = 7.1 × 108 s−1) at 298 and 77 K, respectively, proceeding through an excitation energy migration operating via a Dexter process. Two distinct (Io)1/2 (Io = laser power) dependences of the emission intensity are depicted, indicating saturation as the observed emission increases with the excitation flux. These findings differ from that previously reported isomorphous CP [Cu2Br2(μ-EtS(CH2)4SEt)4]n (CP1), which exhibits no TTA behaviour at 77 K, and only one (laser power)2 dependence at 298 K. The ∼18-fold increase in kQ upon warming CP2 from 77 to 298 K indicates a temperature-aided TTA process. The significant difference between the presence (slower, CP2) and absence (CP1) of TTA at 77 K is explained by the larger unit cell contraction of the former upon cooling. This is noticeable by the larger change in inter-rhomboid Cu⋯Cu separation for CP2.
Disciplines :
Keywords :

Dates :
Data acquisition : 2017
Data provision : 9 Jul 2019
Metadata record :
Creation : 12 Mar 2021

Update periodicity : no update
Language : English (eng)
Additional information :
PDF document contains supplementary information: complete detail of the DFT and TDDFT computations of CP2. CCDC 1886279–1886287.
Audience : Research

Administrative metadata

Data creatorsAffiliation
Adrien SchlachterUniversité de Sherbrooke (CAN)
Antoine BonnotUniversité de Sherbrooke (CAN)
Daniel FortinUniversité de Sherbrooke (CAN)
Paul-Ludovic KarsentiUniversité de Sherbrooke (CAN)
Michael KnorrUTINAM (FRA)
Pierre D. HarveyUniversité de Sherbrooke (CAN)
Publisher : Royal Society of Chemistry
Science contact : Michael Knorr website e-mail
Access : available

Technical metadata

Formats : application/pdf, chemical/x-cif
Data acquisition methods :
Datatype : Dataset


  • Unusual triplet–triplet annihilation in a 3D copper(i) chloride coordination polymer (doi:10.1039/C9CP02891A)
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