Double-Decker Silsesquioxanes Self-Assembled in One-Dimensional Coordination Polymeric Nanofibers with Emission Properties

Abstract

The urgent needs for photoactive materials in industry drive fast evolution of synthetic procedures in many branches of chemistry, including the chemistry of silsesquioxanes. Here, we disclose an effective protocol for the synthesis of novel double-decker silsesquioxanes decorated with two (styrylethynylphenyl)terpyridine moieties ( DDSQ_Ta-b ). The synthesis strategy involves a series of silylative and Sonogashira coupling reactions and is reported for the first time. DDSQ_Ta-b were employed as nanocage ligands to promote self-assembly in the presence of transition metals (TM), i.e., Zn 2+ , Fe 2+ , and Eu 3+ ions, to form one-dimensional (1D) coordination polymeric nanofibers. Additionally, ultraviolet-promoted and reversible E – Z isomerization of the C=C bond within the ligand structures may be exploited to tune their emission properties. These findings render such complexes promising candidates for applications in materials chemistry. This is the first example of 1D coordination polymers bearing DDSQ-based nodes with TM ions.

Distinct insight into the use of difunctional double-decker silsesquioxanes as building blocks for alternating A–B type macromolecular frameworks

“…This behaviour of alkenylsilsesquioxanes has already been reported. 53 It should be also noticed that some of the samples showed the initiation of degradation at low temperatures (below 200 °C). It could be explained by the evaporation of the solvent traces and minor low molecular weight co-monomer residues that probably were occluded in the polymer chains.…”

Hydroxyalkyl-substituted double-decker silsesquioxanes: effective separation ofcisandtransisomers

“…13 C NMR (126 MHz, CDCl 3 ) δ ( ppm): 134.23-127.65 (-Ph), 0.65 (Si-CH 3 ). 29 Si NMR (119 MHz, CDCl 3 ) (cis/trans mixture), δ ( ppm): −32.30 (Si-CH 3 ), −77.30 (2). A threeneck round-bottom flask equipped with a magnetic stirrer and reflux condenser was flashed by pure dinitrogen, and charged with 1 (3.0 g, 2.60 mmol) and anhydrous toluene (200 mL).…”

“…Double-decker silsesquioxanes have shown excellent potential for various applications, including such intriguing areas as materials engineering, smart and self-healing polymers, coordination chemistry, catalysis, and others. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] The structure of a typical double-decker silsesquioxane is different from that of the symmetric cubic T 8 polyhedral oligomeric silsesquioxanes (POSSs). It constitutes an open cage network including two connected, via oxygen bridges, decks of cyclosiloxane rings located on top of one another with eight phenyl groups attached to Si atoms (Fig.…”

Bichromophoric ruthenium(ii) bis-terpyridine-BODIPY based photosensitizers for cellular imaging and photodynamic therapy

“…1,3,5,7-Tetramethyl-8-(4-iodophenyl)-4,4-difluoroboradiaza-indacene and 4′-(4-ethynylphenyl)-2,2′:6′,2″-terpyridine were prepared following reported procedures. 59,60 Detailed descriptions of the materials and instrumentation are provided in the ESI. †…”