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.

Two fluorescent polymers ([Pt]-(AQI(BM-PA) x )) n ([Pt] = trans-bis(ethynylbenzene)-bis-(tributylphosphine)platinum(II); AQI = anthraquinone diimine; BMPA = bis(para-methoxyphenyl)amine), P1 (x = 1; τ F ≤ 8 ps) and P2 (x = 2; τ F = 10 ps, 298 K), were prepared and investigated as thin films in the presence of phenyl-C 61butyric acid methyl ester (PCBM) to probe the photoinduced electron transfer processes using steady-state and timeresolved fluorescence and femtosecond-transient absorption spectroscopy (fs-TAS). P1 and P2 undergo an efficient oxidative photoinduced electron transfer (Px* + PCBM → Px +• + PCBM −• ; x = 1, 2) in solution and as films. Based on fs-TAS, the time scale for the photogenerated charge separated state forms within the excitation pulse (i.e., ≤150 fs). During the course of this study, the nature of the lowest energy emissive excited state was identified as a charge transfer state defined as [Pt] → AQI (major component) and BMPA → AQI (minor component) with the aid of density functional theory (DFT) and time-dependent DFT computations.

The reactivity of the tetradentate ligand bis(p-thiomethylphenylacetylene) (MeSC 6 H 4 C≡C-C≡CC 6 H 4 SMe; L2) towards the CuI salt is compared to that for the known organometallic analogue trans-bis(p-thiomethylethynylbenzene)bis(trimethylphosphine)platinum(II) (trans-Pt(PMe 3) 2 (C≡CC 6 H 4 SMe) 2 ; L1). While L1 with CuI form a highly luminescent porous 2D coordination polymer (CP) of general formula ([Cu 4 I 4 ]L1 • EtCN) n (CP1; Juvenal et al. in Inorg Chem 55:11096-11109, 2016) exhibiting both Cu(η 2-C≡C) and Cu-S bonds, L2 reacts with CuI to produce a luminescent non-porous 2D CP exhibiting the general formula ([Cu 4 I 4 ]{L2} 3) n , CP2, which does not use the highly expected Cu(η 2-C≡C) linkage, relying strictly upon Cu-S coordination. An examination of the X-ray structures for both L2 and CP2 indicates that CP2 network is built upon an expansion of the L2 lattice (plane sliding and slight L2-L2 distance separation) resembling to a sort of template effect. CP2 has been characterized by TGA, UV-Vis, emission spectroscopy, and photophysics, which are accompanied by DFT and TDDFT computations.

The trans-Pt(PMe)(C≡CCHCN) organometallic ligand L1, which is prepared from 4-ethynylbenzonitrile and cis-Pt(PMe)Cl, binds CuX salts to form two strongly luminescent two-dimensional coordination polymers (CPs) [{Cu(μ-X)}(μ-L1)] (X = I, CP1; X = Br, CP2). The emission quantum yields, Φ ≈ 30% at 298 K, are the largest ones for all CPs built upon the trans-Pt(PMe)(C≡CCHX) motifs (X = SMe, CN). X-ray crystallography reveals that, to accommodate these layered CPs, L1 must undergo major distortions of the C≡C-C angles (∼159°) and significant rotations about the Pt-CC bonds, so that the dihedral angles made by the two aromatic planes is 90° in a quasi-identical manner for both CPs. Together, these two features represent the largest distortion for trans-Pt(PMe)(C≡CCHX) complexes among all of the CPs built upon this type of ligand (2 of 16 entries). Concurrently, CP1 and CP2 also exhibit the most red-shifted emissions (λ = 650 and 640 nm, respectively) known for this type of chromophore at room temperature. The {Cu(μ-X)} rhomboids adopt the trans- (X = I, common) and cis-geometries (X = Br, extremely rare) making them "isomers" if excluding the fact that the halides are different. Density functional theory (DFT) and time-dependent DFT suggest that the triplet emissive excited state is metal/halide-to-ligand charge transfer in both cases despite this difference in rhomboid geometry.

The tritopic organometallic ligand trans-MeSC6H4CCPt­(PMe3)2(CN) (L1) was prepared from cis-PtCl2(PMe3)2 and p-ethynyl­(methyl thioether)­benzene. Its versatility was shown with the formation of [CuX­(L1)] n coordination polymers (CPs) with CuX salts in MeCN (X = I (CP1), CN (CP2), SCN (CP3)). These CPs were characterized by X-ray crystallography, thermal gravimetric analysis (TGA), and IR and Raman spectroscopy. CP1 consists of a 1D head-to-tail chain formed by tricoordinated −CN–CuI­(η2-CC)– linkages, whereas CP2 is built upon a central (CuCN) n zigzag chain bearing dangling L1s held by −CN–Cu bonds. Finally, CP3 exhibits 2D sheets secured by Cu–NC–/–(Me)­S–Cu bondings and transversal Cu–S–CN–Cu bridges. Concurrently, the CPs formed with AgX (X = NO3 – (CP4 and CP5), CF3CO2 – (CP6) PF6 – (CP7)) exhibits 2D sheets with guest molecules (anion, solvents) inside the tight pores or between layers. These new materials are emissive: L1 (λ0–0 ∼465 nm), CP1–CP7 (500 < λmax < 620 nm). Their photophysical properties (absorption and emission spectra, emission lifetimes (∼0.2 < τe < 120 μs), and quantum yields in the solid state at 77 and 298 K) were analyzed. The various natures of the emissive excited states were addressed by density functional theory (DFT) and time-dependent DFT (TDDFT) computations. For CP1, this state is a triplet halide or pseudohalide to ligand charge transfer 3XLCT (CT = charge transfer; X = I; L = L1) and for CP2, it is 3XLCT (X = CN; L = L1). However, for CP3, it is 3XLCT (X = SCN; L = L1). For CP4, the T1 state is described as a [MeSC6H4(η2-CC)-Ag­(NO3)]2 → [Pt]/CCC6H4SMe CT.