New Luminescent 1D and 2D d10 Coinage Metal Organic Chalcogenolate Coordination Polymers

Abstract

SSCI-VIDE+CDURABLE+SHA:ABH:ADMInternational audienceCoordination polymers (CPs) with chalcogenate ligands (-Ch-R = S-R, Se-R, Te-R) and d10 coinage metals (M(I) = Cu, Ag and Au ), are well-known for their photoluminescence properties and offer a sustainable opportunity to replace rare earth elements based materials that are considered as critical raw materials by the European union.[1,2] The photoemission of Metals Organic Chalcogenolates (MOCs) is mostly attributed to the presence of d10 coinage metals and their ability to display metallophilic interactions that result in the possibility to fine tune their photophysical properties to get a large palette of color emission with high quantum yields. [3,4]. Herein, we will show the effect of the synthesis protocol on the coordination polymer’s crystal structures and their physical properties. In fact, different exciting crystal structures features were identified from powder and single crystal X-ray diffraction data. Depending on the nature of the synthesis protocol and thiol linker, the structures of the copper MOCs could be centrosymmetric (P21/c) or non-centrosymmetric (Cc, Pca21). The rich variety of the crystal structures impacts directly the photophysical properties with a shift from red to green emission. Moreover, an interesting Second Harmonic Generation response for the non-centrosymmetric compounds was detected, opening a new field of optical applications. [1] H. Furukawa, K. E. Cordova, M. O'Keeffe, O. M. Yaghi, The chemistry and applications of metal-organic frameworks, Science 341 (2013) 1230444. [2] Report on critical raw materials for the EU, May 2014, https://ec. europa.eu/growth/sectors/raw.[3] C. Lavenn; L. Okhrimenko; N. Guillou; M. Monge; G. Ledoux; C. Dujardin; R. Chiriac; A. Fateeva; A. Demessence, J. Mater Chem. C, 2015, 3, 4115.[4] Lavenn; N. Guillou; M. Monge; D. Podbevšek; G. Ledoux; A. Fateeva; A. Demessence, Chem. Commun., 2016, 52, 9063