Abstract
A novel organized di-urethane crossed-linked dodecyl/siloxane (di-alkyl-urethanesil) was synthesized by the sol–gel process and self-directed assembly, from the organosilane precursor (CH3CH2O)3-Si-(CH2)3-NHC( = O)O-(CH2)12-O(O = C)NH-(CH2)3-Si-(OCH2CH3)3, through a fine control of the reaction conditions (hyper-stoichiometric amount of water, minor amount of tetrahydrofuran, and acid catalysis; molar ratio Si:H2O:HCl:THF = 1:300:0.1:12.5). The new bridged silsesquioxane was identified by the notation d-Ut(CY)AC, where Y = 12 is the number of carbon atoms C of the bridging alkyl chains and AC represents acid catalysis. The d-Ut(C12)AC material exhibits a structured lamellar organization with medium long-range order, a texture composed of homogeneous lamellae immersed in a sponge-like matrix made of randomly distributed thin plates, and is thermally stable up to ca. 350 °C. Despite the hydrophobic nature of the dodecane chains, the weakness of the urethane–urethane hydrogen-bonded array formed led to the growth of moderately ordered assemblies of amphiphilic organo(bis-silanetriol) substructures comprising mainly all-trans conformers.
Highlights
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A di-urethane crossed-linked dodecyl/siloxane was produced using a controlled hydrolytic sol–gel route.
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The material exhibits a structured lamellar organization with medium long-range order.
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The morphology of the material includes homogeneous lamellae immersed in a sponge-like matrix.
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The material is thermally stable up to ca. 350 °C.
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References
Liu N, Yu K, Smarsly B, Dunphy DR, Jiang Y-B, Brinker CJ (2002) Self-directed assembly of photoactive hybrid silicates derived from an azobenzene-bridged silsesquioxane. J Am Chem Soc 124:14540–14541
Graffion J, Cattoën X, Wong Chi Man M, Fernandes VR, André PS, Ferreira RAS, Carlos LD (2011) Modulating the photoluminescence of bridged silsesquioxanes incorporating Eu3+-complexed n,n′-diureido-2,2′-bipyridine isomers: application for luminescent solar concentrators. Chem Mater 23:4773–4782
Li C, Wilkes GL (2000) Morphology of inorganic-organic hybrid materials derived from triethoxysilylated diethylenetriamine and tetramethoxysilane. J Macromol Sci Pure Appl Chem 37:549–571
Lu Y, Fan H, Doke N, Loy DA, Assink RA, LaVan DA, Brinker CJ (2000) Evaporation-induced self-assembly of hybrid bridged silsesquioxane film and particulate mesophases with integral organic functionality. J Am Chem Soc 122:5258–5261
Arkles B (1999) Hybrid polymers in the marketplace - mix and match molecular building blocks to create better contact lenses, smoother-sailing ships, slippery surfaces, and move. Chemtech 29:7–14
Lindner E, Auer F, Baumann A, Wegner P, Mayer HA, Bertagnolli H, Reinöhl U, Ertel TS, Weber A (2000) Supported organometallic complexes. Part XX. Hydroformylation of olefins with rhodium(I) hybrid catalysts. J Mol Catal A-Chem 157:97–109
Adima A, Moreau JJE, Man MWC (2000) Immobilization of rhodium complexes in chiral organic–inorganic hybrid materials. Chirality 12:411–420
Hesemann P, Moreau JJE (2000) Novel silica-based hybrid materials incorporating binaphthyl units: a chiral matrix effect in heterogeneous asymmetric catalysis. Tetrahedron: Asymmetry 11:2183–2194
Bied C, Gauthier D, Moreau JJE, Chi Man MW (2001) Preparation and characterization of new templated hybrid materials containing a chiral diamine ligand. J Sol-Gel Sci Technol 20:313–320
Lindner E, Salesch T, Brugger S, Hoehn F, Wegner P, Mayer HA (2002) Supported organometallic complexes: Part XXX. Hydroformylation of 1-hexene in interphases—the influence of different kinds of inorganic–organic hybrid co-condensation agents on the catalytic activity. J Organomet Chem 641:165–172
Creff G, Pichon BP, Blanc C, Maurin D, Sauvajol J-L, Carcel C, Moreau JJE, Roy P, Bartlett JR, Wong Chi Man M, Bantignies J-L (2013) Self-assembly of bridged silsesquioxanes: modulating structural evolution via cooperative covalent and noncovalent interactions. Langmuir 29:5581–5588
Shea KJ, Moreau J, Loy DA, Corriu RJP, Boury B (2005) In: Gómez‐Romero P, Sanchez C (ed) Functional hybrid materials. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Shea KJ, Loy DA (2001) Bridged Polysilsesquioxanes. Molecular-Engineered Hybrid Organic−Inorganic Materials, Chem Mater, 13, 3306–3319
Loy DA, Jamison GM, Baugher BM, Myers SA, Assink RA, Shea KJ (1996) Sol−gel synthesis of hybrid organic−inorganic materials. Hexylene- and phenylene-Bridge polysiloxanes. Chem Mater 8:656–663
Cerveau G, Corriu RJP, Lepeytre C (1997) Organic-inorganic hybrid silica. Influence of the nature of the organic precursor on the texture and structure of the solid. J Organomet Chem 548:99–103
Cerveau G, Corriu RJP (1998) Some recent developments of polysilsesquioxanes chemistry for material science. Coord Chem Rev 178:1051–1071
Cerveau G, Corriu RJP, Framery E (2001) Nanostructured organic-inorganic hybrid materials: kinetic control of the texture. Chem Mater 13:3373–3388
Cerveau G, Corriu RJP, Framery E, Ghosh S, Mutin HP (2002) Hybrid materials and silica: drastic control of surfaces and porosity of xerogels via ageing temperature, and influence of drying step on polycondensation at silicon. J Mater Chem 12:3021–3026
Boury B, Ben F, Corriu RJP (2001) Hydrolysis/polycondensation in the solid state: access to crystalline silica-based hybrid materials. Angew Chem-Int Ed. 40:2853–2856
Moreau JJE, Vellutini L, Chi Man MW, Bied C, Bantignies J-L, Dieudonné P, Sauvajol J-L (2001) Self-organized hybrid silica with long-range ordered lamellar structure. J Am Chem Soc 123:7957–7958
Moreau JJE, Vellutini L, Bied C, Man MWC (2004) New approach for the organisation and the shaping of organo-bridged silicas: an overview. J Sol-Gel Sci Technol 31:151–156
Moreau JJE, Vellutini L, Wong Chi Man M, Bied C, Dieudonné P, Bantignies J-L, Sauvajol J-L (2005) Lamellar bridged silsesquioxanes: self-assembly through a combination of hydrogen bonding and hydrophobic interactions. Chemistry 11:1527–1537
Moreau JJE, Pichon BP, Wong Chi Man M, Bied C, Pritzkow H, Bantignies J-L, Dieudonné P, Sauvajol J-L (2004) A better understanding of the self-structuration of bridged silsesquioxanes. Angew Chem Int Ed 43:203–206
Moreau JJE, Pichon BP, Bied C, Man MWC (2005) Structuring of bridged silsesquioxanes via cooperative weak interactions: H-bonding of urea groups and hydrophobic interactions of long alkylene chains. J Mater Chem 15:3929–3936
Zhou X, Yang S, Yu C, Li Z, Yan X, Cao Y, Zhao D (2006) Hexylene- and octylene-bridged polysilsesquioxane hybrid crystals self-assembled by dimeric building blocks with ring structures. Chemistry 12:8484–8490
Nobre SS, Brites CDS, Ferreira RAS, de Zea Bermudez V, Carcel C, Moreau JJE, Rocha J, Wong Chi Man M, Carlos LD (2008) Photoluminescence of Eu(III)-doped lamellar bridged silsesquioxanes self-templated through a hydrogen bonding array. J Mater Chem 18:4172–4182
Nobre SS, Cattoën X, Ferreira RAS, Carcel C, de Zea Bermudez V, Wong Chi Man M, Carlos LD (2010) Eu3+-assisted short-range ordering of photoluminescent bridged silsesquioxanes. Chem Mater 22:3599–3609
Besson E, Mehdi A, Reye C, Gaveau P, Corriu RJP (2010) Self-assembly of layered organosilicas based on weak intermolecular interactions. Dalton Trans 39:7534–7539
Fernandes M, Nobre SS, Xu QH, Carcel C, Cachia JN, Cattoen X, Sousa JM, Ferreira RAS, Carlos LD, Santilli CV, Man MWC, Bermudez VD (2011) Self-structuring of lamellar bridged silsesquioxanes with long side spacers. J Phys Chem B 115:10877–10891
Nunes SC, Hummer J, Freitas VT, Ferreira RAS, Carlos LD, Almeida P, de Zea Bermudez V (2015) Di-amidosils with tunable structure, morphology and emission quantum yield: the role of hydrogen bonding. J Mater Chem C 3:6844–6861
Fernandes M, Cattoen X, de Zea Bermudez V, Chi Man MW (2011) Solvent-controlled morphology of lamellar silsesquioxanes: from platelets to microsponges. Cryst Eng Comm 13:1410–1415
Pereira RFP, Nunes SC, Toquer G, Cardoso MA, Valente AJM, Ferro MC, Silva MM, Carlos LD, Ferreira RAS, de Zea Bermudez V (2018) Novel highly luminescent amine-functionalized bridged silsesquioxanes. Front Chem 5:31
Nunes SC, de Zea Bermudez V (2018) Structuring of cross-linked non-bridged and bridged amide alkyl-based silsesquioxanes. Chem Rec Accepted for publication, 18, 1–14
Carlos LD, de Zea Bermudez V, Amaral VS, Nunes SC, Silva NJO, Sá Ferreira RA, Rocha J, Santilli CV, Ostrovskii D (2007) Nanoscopic photoluminescence memory as a fingerprint of complexity in self-assembled alkyl/siloxane hybrids. Adv Mater 19:341–348
Nunes SC, Silva NJO, Hummer J, Ferreira RAS, Almeida P, Carlos LD, de Zea Bermudez V (2012) Water-mediated structural tunability of an alkyl/siloxane hybrid: from amorphous material to lamellar structure or bilamellar superstructure. RSC Adv 2:2087–2099
Nunes SC, de Zea Bermudez V, Cybinska J, Sa Ferreira RA, Legendziewicz J, Carlos LD, Silva MM, Smith MJ, Ostrovskii D, Rocha J (2005) Structure and photoluminescent features of di-amide cross-linked alkylene-siloxane hybrids. J Mater Chem 15:3876–3886
Born L, Hespe H (1985) On the physical crosslinking of amine-extended polyurethane urea elastomers: a crystallographic analysis of bis-urea from diphenyl methane-4-isocyanate and 1,4-butane diamine. Colloid Polym Sci 263:335–341
Chang YL, West MA, Fowler FW, Lauher JW (1993) An approach to the design of molecular solids. Strategies for controlling the assembly of molecules into two-dimensional layered structures. J Am Chem Soc 115:5991–6000
de Loos M, van Esch J, Stokroos I, Kellogg RM, Feringa BL (1997) Remarkable stabilization of self-assembled organogels by polymerization. J Am Chem Soc 119:12675–12676
van Esch J, Kellogg RM, Feringa BL (1997) Di-urea compounds as gelators for organic solvents. Tetrahedron Lett 38:281–284
Nunes SC, Bermudez VDZ, Cybinska J, Ferreira RAS, Legendziewicz J, Carlos LD, Silva MM, Smith MJ, Ostrovskii D, Rocha J (2005) Structure and photoluminescent features of di-amide cross-linked alkylene siloxane hybrids. J Mater Chem 15:3876–3886
de Monredon-Senani S, Bonhomme C, Ribot F, Babonneau F (2009) Covalent grafting of organoalkoxysilanes on silica surfaces in water-rich medium as evidenced by Si-29 NMR. J Sol-Gel Sci Technol 50:152–157
Clauss J, Schmidt-Rohr K, Adam A, Boeffel C, Spiess HW (1992) Stiff macromolecules with aliphatic side chains: side-chain mobility, conformation, and organization from 2D solid-state NMR spectroscopy. Macromolecules 25:5208–5214
Parikh AN, Schivley MA, Koo E, Seshadri K, Aurentz D, Mueller K, Allara DL (1997) n-Alkylsiloxanes: from single monolayers to layered crystals. The formation of crystalline polymers from the hydrolysis of n-octadecyltrichlorosilane. J Am Chem Soc 119:3135–3143
Wang R, Baran G, Wunder SL (2000) Packing and thermal stability of polyoctadecylsiloxane compared with octadecylsilane monolayers. Langmuir 16:6298–6305
Earl WL, VanderHart DL (1979) Observations in solid polyethylenes by carbon-13 nuclear magnetic resonance with magic angle sample spinning. Macromolecules 12:762–767
Nakamura N, Setodoi S (1997) 1,12-Dodecanediol. Acta Cryst C 53:1883–1885
Carlos LD, de Zea Bermudez V, Sá Ferreira RA, Marques L, Assunção M (1999) Sol−gel derived urea cross-linked organically modified silicates. 2. Blue-light emission. Chem Mater 11:581–588
Boehm C, Leveiller F, Jacquemain D, Moehwald H, Kjaer K, Als-Nielsen J, Weissbuch I, Leiserowitz L (1994) Packing characteristics of crystalline monolayers of fatty acid salts, at the air-solution interface, studied by grazing incidence x-ray diffraction. Langmuir 10:830–836
Snyder RG, Strauss HL, Elliger CA (1982) Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 1. Long, disordered chains. J Phys Chem 86:5145–5150
MacPhail RA, Strauss HL, Snyder RG, Elliger CA (1984) Carbon-hydrogen stretching modes and the structure of n-alkyl chains. 2. Long, all-trans chains. J Phys Chem 88:334–341
Porter MD, Bright TB, Allara DL, Chidsey CED (1987) Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry. J Am Chem Soc 109:3559–3568
Venkataraman NV, Vasudevan S (2001) Interdigitation of an intercalated surfactant bilayer. J Phys Chem B 105:7639–7650
Venkataraman NV, Bhagyalakshmi S, Vasudevan S, Seshadri R (2002) Conformation and orientation of alkyl chains in the layered organic-inorganic hybrids: (CnH2n+1NH3)2PbI4 (n = 12,16,18). Phys Chem Chem Phys 4:4533–4538
Singh S, Wegmann J, Albert K, Müller K (2002) Variable temperature FT-IR studies of n-alkyl modified silica gels. J Phys Chem B 106:878–888
Brown KG, Bicknell-Brown E, Ladjadj M (1987) Raman-active bands sensitive to motion and conformation at the chain termini and backbones of alkanes and lipids. J Phys Chem 91:3436–3442
Skrovanek DJ, Howe SE, Painter PC, Coleman MM (1985) Hydrogen bonding in polymers: infrared temperature studies of an amorphous polyamide. Macromolecules 18:1676–1683
Coleman MM, Lee KH, Skrovanek DJ, Painter PC (1986) Hydrogen bonding in polymers. 4. Infrared temperature studies of a simple polyurethane. Macromolecules 19:2149–2157
Coleman MM, Skrovanek DJ, Hu J, Painter PC (1988) Hydrogen bonding in polymer blends. 1. FTIR studies of urethane-ether blends. Macromolecules 21:59–65
Cerveau G, Corriu RJP, Dabiens B, Le Bideau J (2000) Synthesis of stable organo(bis-silanetriols): x-ray powder structure of 1,4-bis(trihydroxysilyl)benzene. Angew Chem Int Ed. 39:4533–4537
Brinker CJ (1988) Hydrolysis and condensation of silicates: effects on structure. J Non-Cryst Solids 100:31–50
Wenzel RN (1949) Surface roughness and contact angle. J Phys Colloid Chem 53:1466–1467
Cassie ABD, Baxter S (1944) Wettability of porous surfaces. Soc Faraday Trans 40:546–551
Nunes SC, Ferreira CB, Ferreira RAS, Carlos LD, Ferro MC, Mano JF, Almeida P, de Zea Bermudez V (2014) Fractality and metastability of a complex amide cross-linked dipodal alkyl/siloxane hybrid. RSC Adv 4:59664–59675
Acknowledgements
This work was supported by FEDER, through COMPETE and Fundação para a Ciência e a Tecnologia (FCT) (Pest-OE/QUI/UI0616/2014 and PEst-OE/SAU/UI0709/2014) and LUMECD project (POCI-01-0145-FEDER-016884 and PTDC/CTM-NAN/0956/2014), project UniRCell (Ref. SAICTPAC/0032/2015, POCI-01-0145-FEDER-016422). S.C. Nunes and R.F.P. Pereira acknowledge Post-PhD Fellowships of LUMECD project and SFRH/BPD/87759/2012 grant, respectively.
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Gonçalves, M.C., Pereira, R.F.P., Ferreira, P. et al. Structuring of di-alkyl-urethanesils. J Sol-Gel Sci Technol 89, 205–215 (2019). https://doi.org/10.1007/s10971-018-4703-1
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DOI: https://doi.org/10.1007/s10971-018-4703-1