Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu₂I₂)_n(n = 2, 3) in their coordination polymers

Abstract

Treatment of CuI with the flexible PhS(CH(2))(4)SPh dithioether ligand in MeCN solution affords the strongly luminescent metal-organic 2D coordination polymer [Cu(4)I(4){mu-PhS(CH(2))(4)SPh}(2)](n) (). The interpenetrated 2D network of is built upon by Cu(4)(mu(3)-I)(4) cubane-like clusters as secondary building units (SBUs), which are interconnected via bridging 1,4-bis(phenylthio)butane ligands. In contrast, the auto-assembly reaction of the unsaturated semi-flexible PhSCH(2)C[triple bond, length as m-dash]CCH(2)SPh ligand with CuI results in formation of the 3D metallopolymer [(Cu(6)I(6)){mu-PhSCH(2)C[triple bond, length as m-dash]CCH(2)SPh}(3)](n) (). The SBUs of luminescent consist of discrete Cu(6)(mu(3)-I)(6) hexagon prisms, which are coordinated with bridging 1,4-bis(phenythio)butyne ligands via Cu-S bonds. Contrary to the other rare literature-known examples of metallopolymers incorporating Cu(6)X(6) SBUs as connecting nodes, the CuCu interactions of [2.8484(6) A] are markedly shorter, being close to the sum of the Van der Waals radii of two Cu atoms ( approximately 2.8 A). The photophysics of these compounds, which exhibit reversible luminescence thermochromism, has been investigated in detail. The solid-state luminescence spectra of and feature at room temperature intense emissions around 560 and 555 nm, respectively. The luminescence properties of the unusual Cu(6)(mu(3)-I)(6) hexagon prism motif are rationalized by means of DFT and TDDFT computations.

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

“…[4a,c] However, 2D [{Cu(μ 2 ‐I) 2 Cu}{μ‐PhS(CH 2 ) 3 SPh} 2 ] n and [Cu 4 I 4 {μ‐PhS(CH 2 ) 3 SPh} 2 ] n networks were formed by varying the CuI‐to‐PhS(CH 2 ) 3 SPh ratio. [7a] A double‐interpenetrated 2D network [{Cu(μ 2 ‐I) 2 Cu}{μ‐PhS(CH 2 ) 4 SPh} 2 ] n resulted from treatment of CuI with PhS(CH 2 ) 4 SPh. [7b] Mixing CuI and the dithioether in a 2:1 ratio resulted in the formation of [Cu 4 I 4 {μ‐PhS(CH 2 ) 5 SPh} 2 ] n , in which cubane‐like Cu 4 (μ 3 ‐I) 4 clusters are linked by bridging PhS(CH 2 ) 5 Ph ligands affording a 1D necklace CP similar to that of [Cu 4 I 4 {μ 2 ‐PhSCH 2 SPh} 2 ] n .…”

Luminescent Coordination Polymers Built Upon Cu4X4 (X=Br,I) Clusters and Mono‐ and Dithioethers

“….Cu contacts amount to 2.9645(5) Å in [Cu 6 (m 3 -I) 6 py 6 ] n , and reach even 3.203 Å in [Cu 6 (m 3 -Br) 6 Air-stable 3D material [(Cu 6 I 6 ){m-PhSCH 2 C CCH 2 SPh}] n is also strongly emissive at 298 K and gives rise to an unstructured band at 555 nm after excitation at 360 nm. [53] (Table 4 and Figure 24) and other Cu 4 I 4 -containing species depicted in the literature is striking (where two bands are observed), giving the temptation to propose in both clusters similar assignments for the excited states responsible of the transitions.…”

“…The CuÀI bond lengths range between 2.6391(12) and 2.7745(14) Å (Figure 19). The CuÁÁÁCu distances between the four non-equivalent Cu(I) centers [2.6505 (16) [53] The photophysic properties of the strongly luminescent [Cu 4 I 4 {m-PhS(CH 2 ) 4 SPh} 2 ] n polymer has been examined in detail as well. After excitation at 360 nm, a broad emission with maximum at 560 nm is observed in the solid-state spectrum (Figure 20).…”

“…Its (4,4) topology can be described as undulated square grids, in which the Cu 4 I 4 clusters act as SBUs defining the corners and the dithioether ligands the edges. [53] The side length of each 32-membered square-like macrocycle is %10.6 Å . Moreover, two of these grids are interpenetrated in such a way that the square centers of a net-plane are approximately located on the middle of the edges of the second one.…”

Designs of 3-Dimensional Networks and MOFs Using Mono- and Polymetallic Copper(I) Secondary Building Units and Mono- and Polythioethers: Materials Based on the Cu–S Coordination Bond

“…7, bottom left). The fourth position on the cluster is used for a pentahedral connectivity between the closed cubanes, hence forming an infinite array of cubanes [(Cu 4 I 3 )(l 4 -I)] n along the z-axis, thus making a 3D material The ''semi-rigid'' 1,4-bis(phenylthio)but-2-yne ligand L4 reacts with CuI in MeCN in a 2:1 (or 1:1) molar ratio also to form a colorless polymeric solid of general composition [(Cu 6 I 6 )(L4) 3 ] n [39,40]. X-ray crystallography reveals the presence of 3D network (R3: Fig.…”