The reaction of CuI with the highly flexible dithioether ligand p-TolS(CH2)8STol-p affords both in MeCN or in EtCN the 2D coordination polymers [Cu8I8{p-TolS(CH2)8STol-p}3(solvent)2]n (1·MeCN and 1·EtCN) containing octanuclear Cu8I8 clusters as connection nodes. In contrast, treatment of CuI with p-tBuC6H4S(CH2)8SC6H4But-p in EtCN solution leads to the formation of the luminescent 1D CP [Cu4I4{tBuC6H4S(CH2)8SC6H4-tBu}2(EtCN)2]n (2·EtCN) incorporating Cu4(μ3-I)4 clusters of the closed cubane type as secondary building units (SBUs). The 2D coordination polymers 1·MeCN and 1·EtCN demonstrate the ability to lose their solvent crystallisation molecules under vacuum and readsorb the same or a new one using vapor as monitored by powder X-ray diffraction, thermogravimetric, IR, chromaticity, emission spectra and emission lifetime measurements. Conversely, the 1D material 2·EtCN does not readsorb EtCN, likely due to the collapse of the macrocycles formed by the metal cluster nodes and flexible long-chained ArSC8SAr ligands but absorbs a smaller substrate such as CO2.

The organometallic synthon trans-[p-MeSCHC≡C-Pt(PMe)-C≡CCHSMe] (L1) reacts with CuX (X = Cl, Br, I) in PrCN and PhCN to form 1D- or 2D-coordination polymers (CP) with a very high degree of variability of features. The copper-halide unit can be either the rhomboids CuX fragments or the step cubane CuI. The CP's may also incorporate a crystallization solvent molecule or not, which may be coordinated to copper or not. Their characterizations were performed by X-ray crystallography, thermal gravimetric analysis (TGA), and IR, absorption, and emission spectra as well as photophysical measurements in the presence and absence of solvent crystallization molecules. The nature of the singlet and triplet excited state was addressed using DFT and TDDFT computations, which turn out to be mainly ππ* with some minor MLCT (CuI → L1) contributions. The porosity of the materials has been evaluated by BET (N at 77 K). The solvent-free 1D CP's are not prone to capture solvent molecules or CO, but the efficiency for CO absorption is best for the 2D CP, which exhibits the presence of clear cavities in the grid structure, after the removal of the crystallization molecules.

Two organometallic ligands L1 ( trans -[ p -MeSC 6 H 4 C≡C-Pt(PR 3 ) 2 -C≡CC 6 H 4 SMe; R = Me]) and L2 (R = Et) react with CuX salts (X = Cl, Br, I) in MeCN to form one-dimensional (1D) or two-dimensional (2D) coordination polymers (CPs). The clusters formed with copper halide can either be step cubane Cu 4 I 4 , rhomboids Cu 2 X 2 , or simply CuI. The formed CPs with L1 , which is less sterically demanding than L2 , exhibit a crystallization solvent molecule (MeCN), whereas those formed with L2 do not incorporate MeCN molecules in the lattice. These CPs were characterized by X-ray crystallography, thermogravimetric analysis, IR, Raman, absorption, and emission spectra as well as photophysical measurements in the presence and absence of crystallization MeCN molecules for those CPs with the solvent in the lattice (i.e., [(Cu 4 I 4 ) L1 ·MeCN] n ( CP1 ), [(Cu 2 Br 2 ) L1 ·2MeCN] n ( CP3 ), and [(Cu 2 Cl 2 ) L1 ·MeCN] n ( CP5 )). The crystallization molecules were removed under vacuum to evaluate the porosity of the materials by Brunauer–Emmett–Teller (N 2 at 77 K). The 2D CP shows a reversible type 1 adsorption isotherm for both CO 2 and N 2 , indicative of microporosity, whereas the 1D CPs do not capture more solvent molecules or CO 2 .

EtS(CH)SEt, L1, forms with CuI a luminescent 2D polymer [CuI{μ-L1}] (CP1), which exhibits no triplet excitation energy migration, but with CuBr, it forms a 3D material (CP2), [(CuBr){μ-L1}] consisting of parallel (CuBrS) layers bridged by L1's. CP2 shows T-T annihilation at 298 K but not at 77 K.