- Intramolecular Charge Transfer in Rigidly Linked Naphthalene-Trialkylamine Compounds
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The photophysical properties of two rigidly linked naphthalene-trialkylamine compounds have been examined in a series of solvents using transient absorption spectroscopy and time-resolved spectrofluorimetry.In alkane solvents, excitation of either compound populates a locally excited (naphthalene-like) singlet state (LESS) which fluoresces strongly and which retains a relatively long lifetime.In polar aprotic solvents, the lifetime of the LESS is substantially reduced owing to formation of an intramolecular charge-transfer state (CTS), which corresponds to full electron transfer across the molecule.The rate of formation of the CTS, under such conditions, is extremely fast and comparable to the reorientation time of the solvent.Deactivation of the CTS, which occurs on the nanosecond timescale, involves fluorescence, population of a locally excited triplet state, and charge recombination to restore the ground state.The rate of formation of the CTS is markedly slower in alkanol solvents that can hydrogen bond to the N atom on the donor and, in such cases, charge transfer involves an additional activation energy of ca. 0.12 eV.Under these conditions, it appears that the controlling feature involved in formation of the CTS concerns breakage of a hydrogen bond, whereas in aprotic solvents the intrinsic barrier is likely to be associated with the modest structural changes that might accompany charge transfer.The rates of formation and deactivation of the CTS are discussed briefly in terms of current electron-transfer theory.
- Brun, Anne M.,Harriman, Anthony,Tsuboi, Yasuyuki,Okada, Tadashi,Mataga, Noboru
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- Self-assembled aromatic molecules as efficient organic structure directing agents to synthesize the silicoaluminophosphate SAPO-42 with isolated Si species
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The use of self-assembled aromatic molecules through π-π interactions has allowed the preparation of the silicoaluminophosphate (SAPO) form of the LTA, SAPO-42, with controlled Si content as isolated Si sites in the framework, and high thermal stability. Different SAPO-42 zeotypes can be synthesized with different acidity, morphology, and crystal size, depending on the selected quinolinium derived aromatic molecule as OSDA and the amount of fluoride content in the synthesis gels.
- Martínez-Franco, Raquel,Cantín, ángel,Vidal-Moya, Alejandro,Moliner, Manuel,Corma, Avelino
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p. 2981 - 2989
(2015/05/13)
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- Base-catalysed Rearrangements involvung Ylide Intermediates. Part 8. The Preparation and Some Reactions of Stable Ammonium Ylides
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The carbonyl-stabilised ammonium ylides (3), (12a-n), and (14a-c) were obtained from the reaction of the corresponding ammonium halides (1), (13a-n), and (15a-c) with sodium hydroxide in water or aqueous methanol.The ylides, which were characterised by their molecular formulae and spectroscopic properies, regenerated quaternary ammonium bromides on treatment with hydrobromic acid.In general the reactions of the ammonium ylides resemble those of the corresponding sulphonium ylides.Thus ylides having a suitable migrating group (ArCH2) undergo a Stevens rearrangement on heating, and other ylides fragment to give a tertiary amine and products containing the PhCOCH grouping.A number of ylides reacted with dimethyl acetylenedicarboxylate to give the furans (32).The ylides (14b and c) with phenyl isocyanate gave the phenylcarbamoyl-substituted ylides.
- Jemison, Robert W.,Mageswaran, Sivapathasuntharam,Ollis, W. David,Sutherland, Ian O.,Thebtaranonth, Yodhathai
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p. 1154 - 1164
(2007/10/02)
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