Assembly of Coordination Polymers Using Thioether‐Functionalized Octasilsesquioxanes: Occurrence of (CuX)_n Clusters (X=Br and I) within 3D‐POSS Networks

Abstract

For the first time, POSS-based coordination polymers (CPs) have been structurally characterized. These CPs were obtained in high yield via self-assembly reactions of thioether-functionalized polysilsesquioxanes with Cu salts under mild conditions. Single crystal analyses revealed the formation of 3D networks incorporating different secondary building units (SBUs) as connection nodes. The nature of the -SAr functionality allows a fine-tuning of the cluster nuclearity, that is, butterfly-shaped Cu X or closed cubane-type Cu I cores. As such, the resulting hybrid materials exhibit a combination of high thermal stability arising from the inorganic POSS core along with interesting luminescent properties conferred by the cubane cluster core. Furthermore, the occurrence of channels has been shown crystallographically in the case of the Cu I cluster containing CP.

Smart Transformation of a Polyhedral Oligomeric Silsesquioxane Shell Controlled by Thiolate Silver(I) Nanocluster Core in Cluster@Clusters Dendrimers

“…The Si⋅⋅⋅S distances are about 5.095 Å and angles in S−C−C−C−Si are about 112°, 123°, and 114°, respectively, which is an abnormal distortion (Supporting Information, Figure S2). The Si−O and Si−C distances in the −S−POSS − ligand lie in the range of 1.593–1.611 Å and 1.790–1.811 Å respectively, which are similar to the reported values for POSS complexes . The purity of 1 a is confirmed by its unique MALDI MS spectrum (Supporting Information, Figure S3), showing four characteristic fragmentation products at m / z 5099.2, 4101.9, 3102.8, and 2104.6 owing to [Ag 9 (SSi 8 O 12 C 31 H 69 ) 4 (CF 3 COO) 5 +H] + , [Ag 8 (SSi 8 O 12 C 31 H 69 ) 3 (CF 3 COO) 5 +H] + , [Ag 7 (SSi 8 O 12 C 31 H 69 ) 2 (CF 3 COO) 5 +H] + , and [Ag 6 (SSi 8 O 12 C 31 H 69 )(CF 3 COO) 5 +H] + .…”

“…The readily tunable peripheral groups facilitate the rigid POSS as building blocks for the formation of high‐ordered structures driven by intermolecular interactions such as hydrogen bonding and metal coordination to assemble coordination polymers. Recently, by coordination of thiol−POSS ligand with Cu I complex, a novel structure‐defined 3D complex containing tetranuclear copper(I) cluster as secondary building unit has been demonstrated, indicating that the thiol−POSS is a versatile candidate in the design of metal cluster compounds. Inspired by this, we consider that the thiol‐POSS can be used as protecting shell ligands to induce the formation of new silver(I)–POSS cluster compounds, which have never been reported.…”

A photoactive copper iodide phosphine-based coordination polymer

“…49 The latter displays well resolved peaks but with a similar pattern (envelop) and a close chemical shift value compared with 1. The multiple peaks observed in 2 result from the one-bond J-couplings between the 31 P and the two copper 65 Cu and 63 Cu isotopes (30.8 and 69.2 % of natural abundance, respectively) both having a nuclear spin value of 3/2. In that case, each independent phosphorus atom (two in 2) gives rise to two quartets which overlap in 2.…”

“…Otherwise, only a shift of the single emission band is observed with temperature variation but in any case no vibronic structuration was reported. 31,61,62,63,64…”

Synthesis of metallosupramolecular polymers incorporating cage silsesquioxanes in the main chains

“…Combination of metal complexes with POSS frameworks is attracting interest because optical and magnetic functions would be involved in the POSS containing hybrid materials . Octa‐functionalized POSSs such as octa(3‐aminopropyl)‐ and octa(3‐chloroprpyl) substituted T 8 cages are easily prepared from corresponding trialkoxysilanes.…”