From Short-Bite Ligand Assembled Ribbons to Nanosized Networks in Cu(I) Coordination Polymers Built Upon Bis(benzylthio)alkanes (BzS(CH)SBz; = 1-9).

With the objective to establish a correlation between the spacer distance and halide dependence on the structural features of coordination polymers (CPs) assembled by the reaction between CuX salts (X = Cl, Br, I) and dithioether ligands BzS(CH)SBz ( = 1-9; Bz = benzyl), a series of 26 compounds have been prepared and structurally investigated. A particular attention has been devoted to the design of networks with extremely long and flexible methylene spacer units between the SBz donor sites. Under identical conditions, CuI and CuBr react with BzSCHBz () affording respectively the one-dimensional (1D) CPs {Cu(μ-I)Cu}(μ-)] () and {Cu(μ-Br)Cu}(μ-)] (), which incorporate Cu(μ-X)Cu rhomboids as secondary building units (SBUs).

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}]n (1) is formed when CuI reacts with SMe2 in n-heptane, whereas in acetonitrile (MeCN), the reaction forms exclusively the 2D CP [(Me2S)3{Cu4(μ-I)4}]n (2) 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]n (3) containing "stepped-cubane" Cu4I4 units is isolated in MeCN. In contrast, the reaction in n-heptane affords the 1D CP [(MeSEt)3{Cu4(μ3-I)4}]n (4) containing "closed-cubane" Cu4I4 clusters.

Coordination RC6 H4 S(CH2 )8 SC6 H4 R/(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.

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.

Luminescent P-chirogenic copper clusters.

P-chirogenic clusters of the cubanes [Cu4I4L4] (L = chiral phosphine) were prepared from (+)- and (-)-ephedrine with L = (S)- or (R)-(R)(Ph)(i-Pr)P (with R = CH3 (seven steps) or C17H35 (10 steps)) with e.e. up to 96%.

Organometallic oligomers based on bis(arylacetylide)bis(P-chirogenic phosphine)platinum(II) complexes: synthesis and photonic properties.

A series of P-chirogenic oligomers of the type (-C≡C-aryl-C≡C-PtL2-)n [L = (R)- and (S)-P(Ph)(iPr)(C17H35); aryl = 1,4-benzene, 2,1,3-benzothiadiazole] along the corresponding achiral analogues (L = PBu3) and model complexes PhC≡CPtL2C≡CPh were prepared from the ephedrine strategy and were fully characterized [(1)H, (31)P NMR; IR; small-angle X-ray scattering (SAXS); gel permeation chromatography (GPC); thermal gravimetric analysis (TGA); circular dichroism, UV-vis, and luminescence spectroscopy; photophysics, and degree of anisotropy measurements]. From the CD measurements, the chiral environment of the phosphine ligands is modestly felt by the aryl moieties. Concurrently, the TGA shows that the P(C17H35)(Ph)(i-Pr)-containing materials are more stable than those containing the shorter chain ligand PBu3, and exhibits red-shifted absorption and emission bands compared to those including the PBu3 ligands.

Construction of (CuX)2n cluster-containing (X = Br, I; n = 1, 2) coordination polymers assembled by dithioethers ArS(CH2)(m)SAr (Ar = Ph, p-Tol; m = 3, 5): effect of the spacer length, aryl group, and metal-to-ligand ratio on the dimensionality, cluster nuclearity, and the luminescence properties of the metal-organic frameworks.

Reaction of CuI with bis(phenylthio)propane in a 1:1 ratio yields the two-dimensional coordination polymer [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (1). The 2D-sheet structure of 1 is built up by dimeric Cu(2)I(2) units, which are connected via four bridging 1,3-bis(phenylthio)propane ligands. In contrast, treatment of 2 equiv of CuI with 1,3-bis(phenylthio)propane in MeCN solution affords in a self-assembly reaction the strongly luminescent metal-organic 2D-coordination polymer [Cu(4)I(4){μ-PhS(CH(2))(3)Ph}(2)](n) (2), in which cubane-like Cu(4)(μ(3)-I)(4) cluster units are linked by the dithioether ligands.