Control of Structures and Emission Properties of (CuI)_n 2-Methyldithiane Coordination Polymers

Abstract

A structurally unique and strongly luminescent non-porous 3D coordination polymer (CP) [Cu 8 I 8 (methyldithiane) 4 ] n , CP3, has been prepared in a quasi-anticipated manner from 2-methyl-1,3-dithiane, L1, and CuI. This CP incorporates the unprecedented Cu 8 I 8 cluster built upon two side-fused open cubanes. The crystal structure of CP3 has been determined at 100, 150, 200, 250, 300, 350 and 400 K to study the temperature dependence of the Cu•••Cu distances. Two other topological 1D and 2D CPs isomers of formula [{Cu 2 I 2 }(L1) 2 ] n featuring dinuclear {Cu 2 ( 2 -I) 2 } rhomboids were also obtained independently by control of the reaction conditions. These two CPs convert into CP3 in hot PrCN thus indicating that this latter material is the thermodynamic product. While CP1 and CP2 are not emissive, CP3 exhibits an intense luminescence due to the incorporation of the octanuclear Cu 8 I 8 clusters as secondary building units (SBUs) within the network. The photophysical properties of CP3 have been investigated and rationalized by means of DFT and TDDFT computing. Furthermore, the thermal stability of these materials has been studied by ATG and DSC analyses. The Raman spectra of CP1-3 have been recorded in the solid state in the 50 -500 cm -1 region.

1,3-Dithianes as Assembling Ligands for the Construction of Copper(I) Coordination Polymers. Investigation of the Impact of the RC(H)S2C3H6 Substituent and Reaction Conditions on the Architecture of the 0D–3D Networks

“…Previous studies from our group have shown that the CuI-to-ligand ratio may have a crucial impact on the architecture as well as on nuclearity within the (CuI) n clusters of the resulting network. 48 S17) revealed that no other species is present in the precipitated colorless bulk material. Note also, that in this case and in contrast to L2 (see below), 48 the order of addition of the reactants does not affect the outcome of the reaction.…”

“…48 S17) revealed that no other species is present in the precipitated colorless bulk material. Note also, that in this case and in contrast to L2 (see below), 48 the order of addition of the reactants does not affect the outcome of the reaction.…”

“…[31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] Apart from the fascinating structural richness of these compounds, their photophysical properties, often associated with intense photoluminescence and luminescence thermochromism, 30,46,47 characterized. 48 The chemical structures of the investigated ligands with the dimensionalities and nuclearities of the secondary building units of the resulting CPs are shown in Chart 1.…”

Crystal structures of 9-[bis(benzylsulfanyl)methyl]anthracene and of cyclo-dodecakis(μ2-phenylmethanethiolato-κ2 S:S)hexapalladium(6 Pd—Pd)–anthracene-9,10-dione (1/1)

“…Over the last few years, we have been engaged in exploring the assembly of molecular cluster compounds and coordination polymers using thioether ligands RSCH 2 SR (Peindy et al, 2007;Knorr et al, 2014;Schlachter et al, 2020). Recently, we have also reported the synthesis of Cu I coordination complexes ligated with cyclic thioacetal ligands bearing various substituents (Raghuvanshi et al, 2017(Raghuvanshi et al, , 2019Schlachter et al, 2018;Knauer et al, 2020). Convenient synthetic protocols and interesting luminescent properties displayed by these complexes intrigued us to explore this field further.…”

Crystal structure of the two-dimensional coordination polymer poly[di-μ-bromido-bis(μ-tetrahydrothiophene)dicopper(I)]

“…In the context of our research interest in the assembly of molecular cluster compounds and coordination polymers by complexation of dialkyl sulfides R-S-R or dithiolane-and dithiane-based thiaheterocycles with CuX salts (Knorr et al, 2010(Knorr et al, , 2015Lapprand et al, 2013;Raghuvanshi et al, 2017Raghuvanshi et al, , 2019Schlachter et al, 2018;Knauer et al, 2020), we have also investigated the complexation of CuBr by THT in acetonitrile as solvent (see Fig. 5) and present here the respective crystal structure, which differs both in composition and dimensionality (two-dimensional vs mono-dimensional) from the CP [(CuBr) 2 (THT) 3 ] n reported by Mä lger.…”