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

Two organometallic ligands <b>L1</b> (<i>trans</i>-[<i>p</i>-MeSC₆H₄CC-Pt­(PR₃)₂-CCC₆H₄SMe; R = Me]) and <b>L2</b> (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 <b>L1</b>, which is less sterically demanding than <b>L2</b>, exhibit a crystallization solvent molecule (MeCN), whereas those formed with <b>L2</b> 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)<b>L1</b>·MeCN]<i>_n</i> (<b>CP1</b>), [(Cu₂Br₂)<b>L1</b>·2MeCN]<i>_n</i> (<b>CP3</b>), and [(Cu₂Cl₂)<b>L1</b>·MeCN]<i>_n</i> (<b>CP5</b>)). 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

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

The organometallic synthon <i>trans</i>-[<i>p</i>-MeS­C₆H₄CC-Pt­(PMe₃)₂-CC­C₆H₄­SMe] (<b>L1</b>) 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 Cu₂X₂ fragments or the step cubane Cu₄I₄. 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 (Cu₄I₄ → <b>L1</b>) contributions. The porosity of the materials has been evaluated by BET (N₂ at 77 K). The solvent-free 1D CP’s are not prone to capture solvent molecules or CO₂, but the efficiency for CO₂ 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

1,4-Bis(arylthio)but-2-enes as Assembling Ligands for (Cu₂X₂)_<i>n</i> (X = I, Br; <i>n</i> = 1, 2) Coordination Polymers: Aryl Substitution, Olefin Configuration, and Halide Effects on the Dimensionality, Cluster Size, and Luminescence Properties

CuI reacts with <i>E</i>-PhS­(CH₂CHCHCH₂)­SPh, <b>L1</b>, to afford the coordination polymer (CP) [Cu₂I₂­{μ-<i>E</i>-PhS­(CH₂CHCHCH₂)­SPh}₂]_<i>n</i> (<b>1a</b>). The unprecedented square-grid network of <b>1</b> is built upon alternating two-dimensional (2D) layers with an ABAB sequence and contains rhomboid Cu₂(μ₂-I)₂ clusters as secondary building units (SBUs). Notably, layer A, interconnected by bridging <b>L1</b> ligands, contains exclusively dinuclear units with short Cu···Cu separations [2.6485(7) Å; 115 K]. In contrast, layer B exhibits Cu···Cu distances of 2.8133(8) Å. The same network is observed when CuBr reacts with <b>L1</b>. In the 2D network of [Cu₂Br₂­{μ-<i>E</i>-PhS­(CH₂CHCHCH₂)­SPh}₂]_<i>n</i> (<b>1b</b>), isotype to <b>1a</b>, one square-grid-type layer contains Cu₂(μ₂-Br)₂ SBUs with short Cu···Cu contacts [2.7422(6) Å at 115K], whereas the next layer incorporates exclusively Cu₂(μ₂-Br)₂ SBUs with a significantly longer Cu···Cu separation [2.9008(10) Å]. The evolution of the crystallographic parameters of <b>1a</b> and <b>1b</b> was monitored between 115 and 275 K. Conversely, the isomeric <i>Z</i>-PhS­(CH₂CHCHCH₂)­SPh ligand <b>L2</b> reacts with CuI to form the 2D CP [Cu₄(μ₃-I)₄(μ-<i>­Z</i>-PhS­(CH₂CHCHCH₂)­SPh}₂]_<i>n</i> (<b>2a</b>) with closed-cubane SBUs. A dinuclear zero-dimensional complex [Cu₂Br₂­{μ-<i>Z</i>-PhS­(CH₂CHCHCH₂)­SPh}₂] (<b>2b</b>) is formed when CuBr is reacted with <b>L2</b>. Upon reaction of <i>E</i>-TolS­(CH₂CHCHCH₂)­STol, <b>L3</b>, with CuI, the 2D CP [{Cu­(μ₃-I)}₂­(μ-<b>L3</b>)]_<i>n</i> containing parallel-arranged infinite inorganic staircase ribbons, is generated. When CuX reacts with <i>Z</i>-TolS­(CH₂CHCHCH₂)­STol, <b>L4</b>, the isostructural 2D CPs [Cu₂X₂­{μ-<i>Z</i>-TolS­(CH₂CHCHCH₂)­STol}₂] <b>(4a</b> X = I; <b>4b</b> X = Br) are formed. In contrast to the CPs <b>1a,b</b>, the layers based on rhombic grids of <b>4a,b</b> incorporate Cu₂(μ₂-X)₂ SBUs featuring uniformly identical Cu···Cu distances within each layer. The TGA traces showed that all these materials are stable up to ∼200 °C. Moreover, the photophysical properties have been studied, including absorption, emission, excitation spectra, and emission lifetimes at 298 and 77 K. The spectra were interpreted using density functional theory (DFT) and time-dependent DFT calculations

Reactivity of CuI and CuBr toward Dialkyl Sulfides RSR: From Discrete Molecular Cu₄I₄S₄ and Cu₈I₈S₆ Clusters to Luminescent Copper(I) Coordination Polymers

The 1D coordination polymer (CP) [(Me₂S)₃{Cu₂(μ-I)₂}]_<i>n</i> (<b>1</b>) is formed when CuI reacts with SMe₂ in <i>n</i>-heptane, whereas in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me₂S)₃{Cu₄(μ-I)₄}]_<i>n</i> (<b>2</b>) containing “flower-basket” Cu₄I₄ units. The reaction product of CuI with MeSEt is also solvent-dependent, where the 1D polymer [(MeSEt)₂{Cu₄(μ₃-I)₂(μ₂-I)₂}­(MeCN)₂]_<i>n</i> (<b>3</b>) containing “stepped-cubane” Cu₄I₄ units is isolated in MeCN. In contrast, the reaction in <i>n</i>-heptane affords the 1D CP [(MeSEt)₃{Cu₄(μ₃-I)₄}]_<i>n</i> (<b>4</b>) containing “closed-cubane” Cu₄I₄ clusters. The reaction of MeSPr with CuI provides the structurally related 1D CP [(MeSPr)₃{Cu₄(μ₃-I)₄}]_<i>n</i> (<b>5</b>), for which the X-ray structure has been determined at 115, 155, 195, 235, and 275 K, addressing the evolution of the metric parameters. Similarly to <b>4</b> and the previously reported CP [(Et₂S)₃{Cu₄(μ₃-I)₄}]_<i>n</i> (<i>Inorg. Chem.</i> <b>2010</b>, <i>49</i>, 5834), the 1D chain is built upon closed cubanes Cu₄(μ₃-I)₄ as secondary building units (SBUs) interconnected via μ-MeSPr ligands. The 0D tetranuclear clusters [(L)₄{Cu₄(μ₃-I)₄}] [L = EtSPr (<b>6</b>), Pr₂S (<b>7</b>)] respectively result from the reaction of CuI with EtSPr and <i>n</i>-Pr₂S. With <i>i</i>-Pr₂S, the octanuclear cluster [(<i>i</i>-Pr₂S)₆{Cu₈(μ₃-I)₃}­(μ₄-I)₂}] (<b>8</b>) is formed. An X-ray study has also been performed at five different temperatures for the 2D polymer [(Cu₃Br₃)­(MeSEt)₃]_<i>n</i> (<b>9</b>) formed from the reaction between CuBr and MeSEt in heptane. The unprecedented framework of <b>9</b> consists of layers with alternating Cu­(μ₂-Br)₂Cu rhomboids, which are connected through two μ-MeSEt ligands to tetranuclear open-cubane Cu₄Br₄ SBUs. MeSPr forms with CuBr in heptane the 1D CP [(Cu₃Br₃)­(MeSPr)₃]_<i>n</i> (<b>10</b>), which is converted to a 2D metal–organic framework [(Cu₅Br₅)­(μ₂-MeSPr)₃]_<i>n</i> (<b>11</b>) incorporating pentanuclear [(Cu₅(μ₄-Br)­(μ₂-Br)] SBUs when recrystallized in MeCN. The thermal stability and photophysical properties of these materials are also reported

Reactivity of CuI and CuBr toward Dialkyl Sulfides RSR: From Discrete Molecular Cu₄I₄S₄ and Cu₈I₈S₆ Clusters to Luminescent Copper(I) Coordination Polymers

The 1D coordination polymer (CP) [(Me₂S)₃{Cu₂(μ-I)₂}]_<i>n</i> (<b>1</b>) is formed when CuI reacts with SMe₂ in <i>n</i>-heptane, whereas in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me₂S)₃{Cu₄(μ-I)₄}]_<i>n</i> (<b>2</b>) containing “flower-basket” Cu₄I₄ units. The reaction product of CuI with MeSEt is also solvent-dependent, where the 1D polymer [(MeSEt)₂{Cu₄(μ₃-I)₂(μ₂-I)₂}­(MeCN)₂]_<i>n</i> (<b>3</b>) containing “stepped-cubane” Cu₄I₄ units is isolated in MeCN. In contrast, the reaction in <i>n</i>-heptane affords the 1D CP [(MeSEt)₃{Cu₄(μ₃-I)₄}]_<i>n</i> (<b>4</b>) containing “closed-cubane” Cu₄I₄ clusters. The reaction of MeSPr with CuI provides the structurally related 1D CP [(MeSPr)₃{Cu₄(μ₃-I)₄}]_<i>n</i> (<b>5</b>), for which the X-ray structure has been determined at 115, 155, 195, 235, and 275 K, addressing the evolution of the metric parameters. Similarly to <b>4</b> and the previously reported CP [(Et₂S)₃{Cu₄(μ₃-I)₄}]_<i>n</i> (<i>Inorg. Chem.</i> <b>2010</b>, <i>49</i>, 5834), the 1D chain is built upon closed cubanes Cu₄(μ₃-I)₄ as secondary building units (SBUs) interconnected via μ-MeSPr ligands. The 0D tetranuclear clusters [(L)₄{Cu₄(μ₃-I)₄}] [L = EtSPr (<b>6</b>), Pr₂S (<b>7</b>)] respectively result from the reaction of CuI with EtSPr and <i>n</i>-Pr₂S. With <i>i</i>-Pr₂S, the octanuclear cluster [(<i>i</i>-Pr₂S)₆{Cu₈(μ₃-I)₃}­(μ₄-I)₂}] (<b>8</b>) is formed. An X-ray study has also been performed at five different temperatures for the 2D polymer [(Cu₃Br₃)­(MeSEt)₃]_<i>n</i> (<b>9</b>) formed from the reaction between CuBr and MeSEt in heptane. The unprecedented framework of <b>9</b> consists of layers with alternating Cu­(μ₂-Br)₂Cu rhomboids, which are connected through two μ-MeSEt ligands to tetranuclear open-cubane Cu₄Br₄ SBUs. MeSPr forms with CuBr in heptane the 1D CP [(Cu₃Br₃)­(MeSPr)₃]_<i>n</i> (<b>10</b>), which is converted to a 2D metal–organic framework [(Cu₅Br₅)­(μ₂-MeSPr)₃]_<i>n</i> (<b>11</b>) incorporating pentanuclear [(Cu₅(μ₄-Br)­(μ₂-Br)] SBUs when recrystallized in MeCN. The thermal stability and photophysical properties of these materials are also reported

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)