Luminescent 1D- and 2D-Coordination Polymers Using CuX Salts (X = Cl, Br, I) and a Metal-Containing Dithioether Ligand

Abstract

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.

Co(cyclam) Complexes of Triarylamine-acetylide: Structural and Spectroscopic Properties and DFT Analysis

“…Compared to [ 1 ] + (Figure S1), significant curvature due to the nonlinearity of the Co–C1–C2 and C1–C2–C3 bonds were noted for compounds 2a and 2b and were attributed to η 2 -coordination of Cu­(I) and Ag­(I), respectively. Similar distortions were noted for Pt–CC– polymers coordinated by Cu 2 Y 2 (Y = I, Br, or Cl) in which the Cu-coordinated species had longer CC bonds and bent C–CC bonds …”

“…Similar distortions were noted for Pt−CC− polymers coordinated by Cu 2 Y 2 (Y = I, Br, or Cl) in which the Cucoordinated species had longer CC bonds and bent C−C C bonds. 31 Fourier Transform Infrared Spectra (FTIR). The ATR-FTIR spectra shown in Figure 5 highlight the CC stretching frequencies for [1]Cl, 2a, 2b, and [3]Cl.…”

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

“…The outcome of this study is that the formation of CPs when reacting L1 with CuX salts (X = Cl, Br, I) in various solvents (MeCN, EtCN and PhCN) is that despite the apparent steric constraint around the Pt-center, Cu(η 2 -C≡C) binding is always observed. When Cu-S coordinations also occur, porous or non-porous 2D frameworks are systematically generated [23,24]. This preference for Cu(η 2 -C≡C) linkage over Cu-S is again fully consistent with earlier literature observation mentioned above [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18].…”

“…Second, the secondary building unit (SBU) is a tetranuclear Cu 4 I 4 cluster adopting a staircase structure, which is identical to that observed for the related CP1 built upon L1 (see structure of L1 in Fig. 1) with a general formula ([Cu 4 I 4 ]L1 • solvent) n (solvent = MeCN, EtCN) [23,24]. This trait is somewhat unusual since the structure of the SBU is highly variable going from the rhomboid Cu 2 I 2 , to the closed and open cubane Cu 4 I 4 , to the staircase Cu 4 I 4 , to the hexagonal Cu 6 I 6 , to the closed side-fused dicubane Cu 8 I 8 , to the polymeric staircase (Cu 2 I 2 ) n geometries, just to state a few, and that a slight structural modification of the bridging dithioether ligand can lead to a complete change in SBU and even CP dimensionality [47][48][49].…”

“…Structurally related to L2, a recent investigation on an emissive and rigid organometallic ligand L1 (trans-Pt(PMe 3 ) 2 (C≡CC 6 H 4 SMe) 2 ; Fig. 1) was conducted in order to construct heterobimetallic coordination polymers (CPs) exhibiting both porous frameworks and exhibiting a strong luminescence [23,24]. Figure 1…”