Asuman Çelik KÜÇÜK, Jun MATSUI, Tokujı MIYASHITA

Synthesis of metallo-supramolecular materials based on terpyridine functionalized double-decker silsesquioxane with improved complexation efficienc

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.

Keywords:

Double-decker silsesquioxane, ruthenium II -terpyridine complex, complexation procedures,

PDF

___

1. Matsui J, Kikuchi R, Miyashita T. A trilayer film approach to multicolor electrochromism. Journal of the American Chemical Society 2014; 136 (3): 842-845. doi: 10.1021/ja4107786
2. Davidson RJ, Ainscough EW, Brodie AM, Jameson GB, Waterland MR et al. Terpyridine and 2,6-di(1H-pyrazol-1- yl)pyridine substituted cyclotri- and polyphosphazene ruthenium(II) complexes: Chemical and physical behaviour. Polyhedron 2015; 85: 429-436. doi: 10.1016/j.poly.2014.08.060
3. Li CN, Kwong CY, Djurisic AB, Lai PT, Chui PC et al. Improved performance of OLEDs with ITO surface treatments. Thin Solid Films 2005; 477 (1-2): 57-62. doi: 10.1016/j.tsf.2004.08.111
4. Tanaka H, Mitsuishi M, Miyashita T. Luminescence enhancement of ruthenium complexes in polymer nanosheet by surface plasmon resonance of metal nanoparticle. Chemistry Letters 2005; 34 (9): 1246-1247. doi: 10.1246/cl.2005.1246
5. Fukuda N, Mitsuishi M, Aoki A, Miyashita T. Photocurrent enhancement for polymer Langmuir-Blodgett monolayers containing ruthenium complex by surface plasmon resonance. ýJournal of Physical Chemistry B 2002; 106 (28): 7048-7052. doi: 10.1021/jp014552vCCC:22.00
6. Rubinstein I, Bard AJ. Polymer-films on electrodes. 4. Nafion-coated electrodes and electrogenerated chemiluminescence of surface-attached Ru(Bpy)32+. Journal of the American Chemical Society 1980; 102 (21): 664-6642. doi: 10.1021/ja00541a080
7. Celik A, Kemikli AN, Ozturk R, Muftuoglu AE, Yilmaz F. Synthesis, characterization and thermal properties of a novel star polymer consisting of poly(epsilon-caprolactone) arms emanating from an octa-functional porphyrazine core. Reactive and Functional Polymers 2009; 69 (9): 705-713. doi: 10.1016/j.reactfunctpolym.2009.05.005
8. Kuo SW, Hong JL, Huang YC, Chen JK, Fan SK et al. Star poly(N-isopropylacrylamide) tethered to polyhedral oligomeric silsesquioxane (POSS) nanoparticles by a combination of ATRP and click chemistry. Journal of Nanomaterials 2012; 2012: 749732. doi: 10.1155/2012/749732
9. Pan GR, Mark JE and Schaefer DW. Synthesis and characterization of fillers of controlled structure based on polyhedral oligomeric silsesquioxane cages and their use in reinforcing siloxane elastomers. Journal of Polymer Science Part B 2003; 41 (24): 3314-3323. doi: 10.1002/polb.10695
10. Dodiuk H, Rios PF, Dotan A, Kenig S. Hydrophobic and self-cleaning coatings. Polymers for Advanced Technologies 2007; 18 (9): 746-750. doi: 10.1002/pat.957
11. Kucuk AC. Ion conducting behavior of silsesquioxane-based materials used in fuel cell and rechargeable battery applications. Journal of Structural Chemistry, 2018; 59 (7): 1744-1752. doi: 10.1134/S0022476618070314
12. Miyashita T, Matsui J, Kucuk AC. Proton-conducting membrane based on newly synthesized silsesquioxane derivatives. Japan Patent Office 2015; Japan 5742510.
13. Joshi M, Butola BS. Polymeric nanocomposites - Polyhedral oligomeric silsesquioxanes (POSS) as hybrid nanofiller. Journal of Macromolecular Science-Polymer Reviews 2004; C44 (4): 389-410. doi: 10.1081/MC-200033687
14. Turri S, Levi M. Structure, dynamic properties, and surface behavior of nanostructured ionomeric polyurethanes from reactive polyhedral oligomeric silsesquioxanes. Macromolecules 2005; 38 (13): 5569-5574. doi: 10.1021/ma047304g
15. Haddad TS, Lichtenhan JD. Hybrid organic-inorganic thermoplastics: Styryl-based polyhedral oligomeric silsesquioxane polymers. Macromolecules 1996; 29 (22): 7302-7304. doi: 10.1021/ma960609d
16. Sanchez C, Soler-Illia GJDA, Ribot F, Lalot T, Mayer CR et al. Designed hybrid organic-inorganic nanocomposites from functional nanobuilding blocks. Chemistry of Materials 2001; 13 (10): 3061-3083. doi: 10.1021/cm011061e
17. Au-Yeung HL, Tam AYY, Leung SYL, Yam VWW. Supramolecular assembly of platinum-containing polyhedral oligomeric silsesquioxanes: An interplay of intermolecular interactions and a correlation between structural modifications and morphological transformations. Chemical Science 2017; 8 (3): 2267-2276. doi: 10.1039/C6SC04169H
18. Koytepe S, Demirel MH, Gultek A, Seckin T. Metallo-supramolecular materials based on terpyridine-functionalized polyhedral silsesquioxane. Polymer International 2014; 63 (4): 778-787. doi: 10.1002/pi.4596
19. Murfee HJ, Thoms TPS, Greaves J, Hong B. New metallodendrimers containing an octakis(diphenylphosphino)- functionalized silsesquioxane core and ruthenium(II)-based chromophores. Inorganic Chemistry 2000; 39 (23): 5209-5217. doi: 10.1021/ic000490w
20. Kucuk AC, Matsui J, Miyashita T. Synthesis and photochemical response of Ru(II)-coordinated double-decker silsesquioxane. RSC Advances 2018; 8 (4): 2148-2156. doi: 10.1039/C7RA12290J
21. Kucuk AC, Matsui J, Miyashita T. Effects of hydrogen bonding on the monolayer properties of amphiphilic doubledecker-shaped polyhedral silsesquioxanes. Langmuir 2011; 27 (10): 6381-6388. doi: 10.1021/la200604w
22. Kucuk AC, Matsui J, Miyashita T. Langmuir-Blodgett films composed of amphiphilic double-decker shaped polyhedral oligomeric silsesquioxanes. Journal of Colloid and Interface Science 2011; 355 (1): 106-114. doi: 10.1016/j.jcis.2010.12.033
23. Kucuk AC, Matsui J, Miyashita T. Proton-conducting electrolyte film of double-decker-shaped polyhedral silsesquioxane containing covalently bonded phosphonic acid groups. Journal of Materials Chemistry A 2012; 22 (9): 3853- 3858. doi: 10.1039/C2JM15779A
24. Kucuk AC, Matsui J, Miyashita T. Effects of subphase composition on the monolayer behavior of “core-coronae” type hybrid amphiphiles. Thin Solid Films 2013; 534: 577-583. doi: 10.1016/j.tsf.2013.02.029