A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties (2020)

[1] : Départment de Chimie - Université de Sherbrooke
[2] : Technische Universität Dortmund
[3] : Institut UTINAM (UMR 6213) (Université de Franche-Comté)
[4] : Observatoire des Sciences de l'Univers - Terre, Homme, Environnement, Temps, Astronomie (UAR 3245) (Université de Franche-Comté)
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 :

General metadata

Data acquisition date : from 2016 to 2021
Data acquisition methods :
Update periodicity : no update
Language : English (eng)
Formats : application/pdf, chemical/x-cif
Audience : Research


Spectral coverage :

Publications :
  • A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties (doi:10.1021/acs.inorgchem.1c01856)
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)
Additional information :
PDF document contains supplementary information: complete detail of the DFT and TDDFT computations of CP2
Record created 30 Sep 2021 by Michael Knorr.
Local identifier: FR-18008901306731-2021-09-30.


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Université de Bourgogne, Université de Franche-Comté, UTBM, AgroSup Dijon, ENSMM, BSB, Arts des Metiers