Novel amide cross-linked alkylene–siloxane hybrid materials (di-amidosils) synthesized by the sol–gel process have been investigated. Two samples identified by the notation d-A(x) with x = 4 and 8 (where x is the number of methylene groups of the alkylene chain) have been produced as transparent, amorphous, rigid monoliths. The d-A(8) material is thermally stable up to approximately 245 °C. In this hybrid the siliceous framework is mainly composed of [–(CH₂)Si(OSi)₃)] and [–(CH₂)Si(OSi)₂(OH)] substructures. Structural unit distances of 4.1 and 4.2 Å and average interparticle distances of 12 and 17 Å have been determined for d-A(4) and d-A(8), respectively. In these compounds the alkylene chains are disordered and adopt gauche conformations. While a negligible proportion of the amide linkages remain non-bonded, the great majority of these groups belong to highly disordered strong hydrogen-bonded amide–amide associations. The hybrids introduced are room temperature white light emitters, presenting an intense, broad emission band in the blue/purplish-blue spectral region. The origin of such a band has been ascribed to the convolution of donor–acceptor pair (D–A) recombinations that occur in the NH groups of the amide linkages and in the siliceous nanodomains. The maximum quantum yield value of the d-A(8) di-amidosil is 5.4%.

Poly(oxyethylene) (POE)/siloxane hybrids (di-ureasils) doped with a wide concentration range of lithium triflate <mml:math display="inline"><mml:mo stretchy="false">(</mml:mo><mml:msub><mml:mi mathvariant="normal">LiCF</mml:mi><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mo>SO</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:mo stretchy="false">)</mml:mo></mml:math>(LiCF3SO3) were investigated. The host matrix of these materials [d-U(2000)] is a sol-gel-derived siliceous framework to which POE chains with about 40.5 repeat units are bonded through urea linkages. Xerogels with <mml:math display="inline"><mml:mo>∞</mml:mo><mml:mo>⩾</mml:mo><mml:mi>n</mml:mi><mml:mo>⩾</mml:mo><mml:mn>5</mml:mn></mml:math>∞⩾n⩾5 (n is the molar ratio <mml:math display="inline"><mml:msub><mml:mo>OCH</mml:mo><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mo>CH</mml:mo><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub><mml:mo>/</mml:mo><mml:msup><mml:mi mathvariant="normal">Li</mml:mi><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msup><mml:mo stretchy="false">)</mml:mo></mml:math>OCH2CH2/Li+) were obtained as amorphous monoliths thermally stable up to at least 340°C. A crystalline <mml:math display="inline"><mml:mo>POE</mml:mo><mml:mo>/</mml:mo><mml:msub><mml:mi mathvariant="normal">LiCF</mml:mi><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mo>SO</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub></mml:math>POE/LiCF3SO3 complex was detected spectroscopically in samples with <mml:math display="inline"><mml:mi>n</mml:mi><mml:mo>⩽</mml:mo><mml:mn>10</mml:mn><mml:mo>.</mml:mo></mml:math>n⩽10. Below 90°C the ormolyte with <mml:math display="inline"><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn>20</mml:mn></mml:math>n=20 exhibits the highest conductivity <mml:math display="inline"><mml:mo stretchy="false">(</mml:mo><mml:mn>5.8</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mrow><mml:mn>10</mml:mn></mml:mrow><mml:mrow><mml:mo>−</mml:mo><mml:mn>6</mml:mn></mml:mrow></mml:msup></mml:math>(5.8×10−6 Ω⁻¹ cm⁻¹ at 26°C). The redox stability domain of this material spans 4.1 V. Although Fourier transform infrared spectroscopy data suggest that the <mml:math display="inline"><mml:msup><mml:mi mathvariant="normal">Li</mml:mi><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math>Li+ ions are complexed by the POE ether oxygen atoms at <mml:math display="inline"><mml:mi>n</mml:mi><mml:mo>⩽</mml:mo><mml:mn>10</mml:mn><mml:mo>,</mml:mo></mml:math>n⩽10, this threshold composition is probably located at slightly lower salt content. “Free” triflate ions and weakly coordinated anions, present in all the samples examined, must be the main charge carriers of the <mml:math display="inline"><mml:mi mathvariant="normal">d</mml:mi><mml:mo>­</mml:mo><mml:mo>U</mml:mo><mml:mo stretchy="false">(</mml:mo><mml:mn>2000</mml:mn><mml:msub><mml:mo stretchy="false">)</mml:mo><mml:mrow><mml:mn>20</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mi mathvariant="normal">LiCF</mml:mi><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mo>SO</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub></mml:math>d­U(2000)20LiCF3SO3 xerogel. Ion pairs <mml:math display="inline"><mml:mo stretchy="false">(</mml:mo><mml:msup><mml:mi mathvariant="normal">Li</mml:mi><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msup><mml:msub><mml:mo>CF</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:msubsup><mml:mo>SO</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow><mml:mrow><mml:mo>−</mml:mo></mml:mrow></mml:msubsup><mml:mo stretchy="false">)</mml:mo></mml:math>(Li+CF3SO3−) or negatively charged triplets <mml:math display="inline"><mml:mo stretchy="false">(</mml:mo><mml:mo stretchy="false">[</mml:mo><mml:mi mathvariant="normal">Li</mml:mi><mml:mo stretchy="false">(</mml:mo><mml:msub><mml:mo>CF</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mo>SO</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mo stretchy="false">)</mml:mo><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub><mml:msup><mml:mo stretchy="false">]</mml:mo><mml:mrow><mml:mo>−</mml:mo></mml:mrow></mml:msup><mml:mo stretchy="false">)</mml:mo></mml:math>([Li(CF3SO3)2]−) are formed at <mml:math display="inline"><mml:mi>n</mml:mi><mml:mo>⩽</mml:mo><mml:mn>40</mml:mn><mml:mo>.</mml:mo></mml:math>n⩽40. At <mml:math display="inline"><mml:mi>n</mml:mi><mml:mo>⩽</mml:mo><mml:mn>5</mml:mn></mml:math>n⩽5 positively charged triplets <mml:math display="inline"><mml:mo stretchy="false">[</mml:mo><mml:msub><mml:mi mathvariant="normal">Li</mml:mi><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub><mml:mo stretchy="false">(</mml:mo><mml:msub><mml:mo>CF</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mo>SO</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:mo stretchy="false">)</mml:mo><mml:msup><mml:mo stretchy="false">]</mml:mo><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math>[Li2(CF3SO3)]+ also appear. Divalent positively charged multiplets <mml:math display="inline"><mml:mo stretchy="false">[</mml:mo><mml:msub><mml:mi mathvariant="normal">Li</mml:mi><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:mo stretchy="false">(</mml:mo><mml:msub><mml:mo>CF</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mo>SO</mml:mo><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub><mml:mo stretchy="false">)</mml:mo><mml:msup><mml:mo stretchy="false">]</mml:mo><mml:mrow><mml:mn>2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math>[Li3(CF3SO3)]2+ occur at <mml:math display="inline"><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn>1</mml:mn><mml:mo>.</mml:mo></mml:math>n=1. © 2005 The Electrochemical Society. All rights reserved.