Abstract
Ordered mono-amide cross-linked alkyl/siloxane hybrids (mono-amidosils) incorporating a Rhodamine (B) methyl ester perchlorate dye (Rh(B)CH3ClO4) have been synthesized through the sol–gel process and self-directed assembly. The host hybrid matrix m-A(14) is a lamellar bilayer hierarchically structured hybrid composed of short methyl-capped alkyl chains grafted to a siliceous framework through amide groups. At low dye concentration [n = 20, where n is the molar ratio of amide groups per Rh(B)CH3ClO4] a new lamellar structure with higher interlamellar distance than that of m-A(14) is formed, whereas at higher dye content (n = 5) this new lamellar structure coexists with that of m-A(14). The efficient encapsulation of Rh(B)CH3ClO4 provided by m-A(14) via hydrogen bonding interactions ensured the complete dissolution of the dye and induced a blue shift of the emission of the dye with respect to that of the isolated state, leading to an increase in the quantum yield from values below 0.01 % (measured for the isolated dye) to 4 % at n = 20. The formation of non-fluorescent H-type dimers in the sample with n = 5 accounts for the reduction of the quantum yield. The incorporation of Rh(B)CH3ClO4) into m-A(14) was clearly beneficial from the standpoint of the dye’s photostability, allowing to suppress photobleaching during the first 4 h. An intensification of the emission intensity by 50 and 25 % for the emission centered at 600 and 645 nm resulted, respectively, at n = 20.
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Acknowledgments
This work was supported by Fundação para a Ciência e a Tecnologia (FCT) and FEDER (contracts PTDC/QUI-QUI/100896/2008, PTDC/CTM-BPC/112774/2009, Pest-C/SAU/UI0709/2011, and Pest-14C/CTM/LA0011/2013). The support of COST Action MP1202880 “Rational design of hybrid organic–inorganic interfaces” is also acknowledged. S. C. Nunes and V. T. Freitas thank FCT for Grants (SFRH/BPD/63152/2009 and SFRH/BD/87403/2012, respectively).
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Nunes, S.C., Freitas, V.T., Ferreira, R.A.S. et al. Lamellar mono-amidosil hybrids doped with Rhodamine (B) methyl ester perchlorate. J Sol-Gel Sci Technol 72, 239–251 (2014). https://doi.org/10.1007/s10971-014-3339-z
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DOI: https://doi.org/10.1007/s10971-014-3339-z