Antoine Bonnot

Slow and Fast Singlet Energy Transfers in BODIPY-gallium(III)corrole Dyads Linked by Flexible Chains

Red (no styryl), green (monostyryl), and blue (distyryl) BODIPY-gallium(III) (BODIPY = boron-dipyrromethene) corrole dyads have been prepared in high yields using click chemistry, and their photophysical properties are reported. An original and efficient control of the direction of the singlet energy transfers is reported, going either from BODIPY to the gallium-corrole units or from gallium-corroles to BODIPY, depending upon the nature of the substitution on BODIPY. In one case (green), both directions are possible. The mechanism for the energy transfers is interpreted by means of through-space Förster resonance energy transfer (FRET).

Formation of an unprecedented (CuBr)5 cluster and a zeolite-type 2D-coordination polymer: a surprising halide effect

A unique pentanuclear cluster within a zeolite-type polymer ([Cu5(μ4-Br)(μ3-Br)2(μ2-Br)2](μ2-MeSPr)3)n (1; void space >81%) and a luminescent 1D ([Cu(μ3-I)]4(MeSPr)3)n polymer, 2, are formed when MeSPr reacts with CuBr and CuI.

Coordination RC6H4S(CH2)8SC6H4R/(CuI)n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

Under identical conditions, CuI reacts with PhS(CH2 )8 SPh and p-TolS(CH2 )8 STol-p affording, respectively, a luminescent 1D coordination polymer [Cu4 I4 {μ2 -PhS(CH2 )8 SPh}2 ]n (1) and an unprecedented 2D network [Cu8 I8 {μ2 -p-TolS(CH2 )8 STol-p}3 (MeCN)2 ]n (2), which incorporate closed-cubane Cu4 I4 and octanuclear Cu8 I8 clusters of as connecting nodes. Their thermal and photophysical properties exhibit notable differences.

The trans-Bis(p-thioetherphenylacetynyl)bis(phosphine)platinum(II) Ligands: A Step towards Predictability and Crystal Design

Two organometallic ligands L1 (trans-[p-MeSC6H4C≡C-Pt(PR3)2-C≡CC6H4SMe; 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 Cu4I4, rhomboids Cu2X2, 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., [(Cu4I4)L1·MeCN]n (CP1), [(Cu2Br2)L1·2MeCN]n (CP3), and [(Cu2Cl2)L1·MeCN]n (CP5)). The crystallization molecules were removed under vacuum to evaluate the porosity of the materials by Brunauer–Emmett–Teller (N2 at 77 K). The 2D CP shows a reversible type 1 adsorption isotherm for both CO2 and N2, indicative of microporosity, whereas the 1D CPs do not capture more solvent molecules or CO2.

The 3D [(Cu2Br2){μ-EtS(CH2)4SEt}]n material: a rare example of a coordination polymer exhibiting triplet–triplet annihilation

EtS(CH2)4SEt, L1, forms with CuI a luminescent 2D polymer [Cu4I4{μ-L1}2]n (CP1), which exhibits no triplet excitation energy migration, but with CuBr, it forms a 3D material (CP2), [(Cu2Br2){μ-L1}]n consisting of parallel (Cu2Br2S2)n layers bridged by L1s. CP2 shows T1-T1 annihilation at 298 K but not at 77 K.

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

The reactivity of the tetradentate ligand bis(p-thiomethylphenylacetylene) (MeSC6H4C≡C–C≡CC6H4SMe; L2) towards the CuI salt is compared to that for the known organometallic analogue trans-bis(p-thiomethylethynylbenzene)bis(trimethyl-phosphine)platinum(II) (trans-Pt(PMe3)2(C≡CC6H4SMe)2; L1). While L1 with CuI form a highly luminescent porous 2D coordination polymer (CP) of general formula ([Cu4I4]L1 · EtCN)n (CP1; Juvenal et al. in Inorg Chem 55:11096–11109, 2016) exhibiting both Cu(η2–C≡C) and Cu–S bonds, L2 reacts with CuI to produce a luminescent non-porous 2D CP exhibiting the general formula ([Cu4I4]{L2}3)n, CP2, which does not use the highly expected Cu(η2–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.Graphical abstract