Dataset : A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

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Quotation

Adrien Schlachter ; Kevin Tanner ; Rebecca Scheel ; Paul-Ludovic Karsenti ; Carsten Strohmann ; Michael Knorr ; Pierre D. Harvey (2020): A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties. American Chemical Society. ccdc:2048036

General metadata

Identifiers : local : FR-18008901306731-2021-09-30 external : ccdc:2048036, ccdc:2048037, ccdc:2048041, ccdc:2048042, ccdc:2048044, ccdc:2048045, ccdc:2048050, doi:10.1021/acs.inorgchem.1c01856
Description :
The design of new and inexpensive metal-containing functional materials is of great interest. Herein is reported a unique thermochromic near-IR emitting coordination polymer, 3D-[Cu8I8(L1)2]n, CP2, which is formed when ArS(CH2)4SAr (L1, Ar = 4-C6H4OMe) reacts with 2 equiv of CuI in EtCN. In MeCN, CP1 ([Cu4I4(L1)(MeCN)2]n, consisting of an alternating [-Cu4I4-L1-Cu4I4-L1-]n chain where the Cu4I4 cubane units bear two metal-bound MeCN molecules, is formed. Heat-driven elimination of these MeCN’s in solid CP1 also leads to CP2 through a predisposed organization of the Cu4I4 units prone to fusion after MeCN eliminations (i.e., a rare case of template effect). The CP2 structure exhibits parallel 1D-(Cu8I8)n chains, (z-axis; designated 1D-[CuI]n) as secondary building units (SBU) held together by parallel thioether ligands (x,y-axes), forming a nonporous 3D network. The structure of this 1D-[CuI]n SBU is unprecedented and consists of a series of fused and twisted open Cu4I4 cubanes forming a fused poly(truncated rhombic dodecahedron). Unexpectedly, the compact 3D CP2 exhibits a solid-to-solid phase transition at 100 °C and a hysteresis of ∼20 °C. CP1 emits intensively (298 K: λemi = 564 nm; Φe = 0.35), whereas CP2 presents a strongly red-shifted weaker emission (298 K: λemi ∼ 740 nm, Φe < 0.0001). Moreover, CP2, which is stable over long periods of time, exhibits thermochromism where the emission intensity of the near-IR band decreases significantly at the benefit of a ligand-centered phosphorescence at 415 nm. Altogether, these properties listed above make CP2 exceptional. The low-energy singlet and triplet excited states have been assigned to ligand/metal-to-ligand charge transfer based on DFT and TD-DFT computations.
Disciplines :
Keywords :

Dates :
Data acquisition : from 2016 to 2021
Data provision : 3 Dec 2020
Metadata record :
Creation : 30 Sep 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
Audience : Research

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Spectral coverage :

Administrative metadata

Data creatorsAffiliation
Adrien SchlachterUniversité de Sherbrooke (CAN)
Kevin TannerUniversité de Sherbrooke (CAN)
Rebecca ScheelTU Dortmund (DEU)
Paul-Ludovic KarsentiUniversité de Sherbrooke (CAN)
Carsten StrohmannTU Dortmund (DEU)
Michael KnorrUTINAM (FRA)
Pierre D. HarveyUniversité de Sherbrooke (CAN)
Publisher : American Chemical Society
Science contact : Michael Knorr website e-mail
Project and funders :
  • Elaboration des matériaux luminescents
    • Centre Québecois sur les Matériaux Fonctionnels (Another international)
    • Compute Canada and Calcul Québec (Another international)
    • Fonds de Recherche du Québec-Nature et Technologies (Another international)
    • Natural Sciences and Engineering Research Council of Canada (Another international)
Access : available

Technical metadata

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

Publications

  • A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties (doi:10.1021/acs.inorgchem.1c01856)
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