Synthesis and photochemical response of Ru(<scp>ii</scp>)-coordinated double-decker silsesquioxane

Silsesquioxane-based transition-metal complexes have come to the forefront due to the ability of silsesquioxane to control nanostructures and properties. However, some difficulties in complete complexation and purification limit the widespread use of transition-metal-based supramolecular coordination complexes comprising silsesquioxane. Herein, 2 different approaches have been proposed for the synthesis of metallo-supramolecular materials on the basis of ruthenium(II)-terpyridine functional double-layer silsesquioxane (DDSQ) (Tpy/Ru-DDSQ) (Routes 1 and 2). In Route 1, complexation was followed by functionalization of DDSQ with the ligand, whereas in Route 2, complexation was performed before the ligand was inserted into the DDSQ. Tpy/Ru-DDSQ obtained from both approaches was characterized by 1 H NMR, X-ray photoelectron spectrometer, and FTIR and found in the same structure. Both methods were fully discussed and their merits were explored. The complexation yield of the routes was similar. However, the results based on NMR and UV-Vis spectroscopy demonstrated that the incorporation rate of DDSQ into the complex was quite high in Route 2. As far as is known, this is the first study based on the effects of complexing Tpy ligands before/after binding to the target compound, particularly to silsesquioxane-based materials.

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“…The pure product was obtained in a 95% yield. The characterization results obtained were fully consistent with a previous study [20].…”

Section: Synthesis Of Ddsq-based Ru(ii)-tpy Complex Through Route 1 2supporting

confidence: 91%

ynthesis of metallo-supramolecular materials based on terpyridine functionalizeddouble-decker silsesquioxane with improved complexation efficiency

Küçük¹,

Matsui²,

Miyashita³

2020

Turk J Chem

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“…The utilization of silsesquioxanes in the synthesis of hybrid materials with enhanced thermal, mechanical, or dielectric properties is of fundamental importance. [41] Our group have also reported the use of DDSQ-4OSiH as an efficient hydrosilylating agent of aliphatic dienes. Again, this is reflected in the number of papers and patents published each year.…”

Section: Introductionmentioning

confidence: 96%

“…Miyashita et al also presented allyl glycidyl ether as modifying agent of DDSQ-4OSiH via HS to form precursor applied in immobilization of Ru II terpyridine DDSQ based complex. [41] Our group have also reported the use of DDSQ-4OSiH as an efficient hydrosilylating agent of aliphatic dienes. [42] The reported studies basically were focused on the synthesis and further application of properly tetrasubstituted DDSQ-based silsesquioxanes.…”

Section: Introductionmentioning

confidence: 96%

“…At the same time, chemists are looking for synthetic routes exploiting among others hydrosilylation reaction to obtain novel, functionalized Si-based reagents with a specific structure such as silsesquioxanes. [17][18][19][20][21][22][23][24][25][26][27] While hydrosilylation of olefins with silanes has been widely studied, [3,28] the reports on T 8 silsesquioxanes are limited [5,6,[29][30][31][32][33][34] and for double-decker systems of both closed (D 2 T 8 [4,19,25,[35][36][37] ) and opened (M 4 T 8 [38][39][40][41][42][43] ) structure even more scant. [5] Cage-like derivatives have driven much attention due to specific physicochemical properties (governed by the nature of their silicate rigid core and by the number and type of functional groups attached to it) affecting directions of their broad applications from material chemistry to medicine.…”

Section: Introductionmentioning

confidence: 99%

“…[12,15,16] Taking research in the field of macromolecular DDSQ-based frameworks of hybrid nature into account, difunctionalized doubledecker silsesquioxanes are of greatest interest due to the possibility of their incorporation into the main chain of the polymer. [17][18][19][20][21][22][23][24][25][26][27] While hydrosilylation of olefins with silanes has been widely studied, [3,28] the reports on T 8 silsesquioxanes are limited [5,6,[29][30][31][32][33][34] and for double-decker systems of both closed (D 2 T 8 [4,19,25,[35][36][37] ) and opened (M 4 T 8 [38][39][40][41][42][43] ) structure even more scant. Miyashita and co-workers were the first to apply hydrosilylation as a method to modify tetrahydrosubstituted DDSQ (DDSQ-4OSiH) compound with N-vinylcarbazole performed in the presence of Karstedt's catalyst.…”

Section: Introductionmentioning

confidence: 99%

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Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

et al. 2019

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We present an efficient methodology for the synthesis of tetrafunctionalized double-decker silsesquioxanes via hydrosilylation reaction. An investigation of the catalytic system, olefin structure, chemical and steric surrounding of SiÀ H moiety in the respective reagent was carried out on the progress, selectivity and rate of hydrosilylation process. Two alternative synthetic pathways for obtaining a variety of functionalized double-decker silsesquioxanes with high yields based on the Pt catalysts were developed. These parallel routes concern reverse SiÀ H and À CH=CH 2 reactive groups placement in the doubledecker silsesquioxane core. As a result, a series of new tetrasubstituted double-decker silsesquioxanes derivatives were obtained with high yield and selectivity and comprehensively characterized in detail by spectroscopic analyses.[a] J.

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Synthesis of a “Butterfly Cage” Based on a Double‐Decker Silsesquioxane

Kunthom

Adachi

Liu

et al. 2019

Chemistry An Asian Journal

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Novel polyhedral structures were prepared with a butterfly‐shape composed of oligosiloxane wings and a double‐decker silsesquioxane (DDSQ) body. The compounds were synthesized in two steps from commercially available alkoxysilanes, and their structures were confirmed using spectroscopic methods and X‐ray crystallography. Not like other phenyl‐substituted cage silsesquioxanes, these butterfly cages show very good solubility in common organic solvents. The crystal structures clearly showed their unique features: a larger space with longer siloxane chains and a very flexible framework. Moreover, these compounds are thermally stable with a Td5 (5 % weight loss temperature) over 320 °C.

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Synthesis and photochemical response of Ru(ii)-coordinated double-decker silsesquioxane

Abstract: A double-decker-silsesquioxane (DDSQ) based transition-metal-complex showed efficient energy-conversion owing to the assembling ability of the complexes in the DDSQ nano-building blocks.

Cited by 19 publications

References 37 publications

ynthesis of metallo-supramolecular materials based on terpyridine functionalizeddouble-decker silsesquioxane with improved complexation efficiency

ynthesis of metallo-supramolecular materials based on terpyridine functionalizeddouble-decker silsesquioxane with improved complexation efficiency

Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

Synthesis of a “Butterfly Cage” Based on a Double‐Decker Silsesquioxane

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