https://hdl.handle.net/11000/7 2026-09-28T18:24:58Z 2026-09-28T18:24:58Z El-Khouly, Mohamed E. Gutiérrez, Ana Mª Sastre-Santos, Ángela Fernández-Lázaro, Fernando Fukuzumi, Shunichi https://hdl.handle.net/11000/40848 2026-09-28T18:14:21Z 2026-09-28T18:14:21Z

Título : Light harvesting zinc naphthalocyanine–perylenediimide supramolecular dyads: long-lived charge-separated states in nonpolar media - Autor : El-Khouly, Mohamed E.; Gutiérrez, Ana Mª; Sastre-Santos, Ángela; Fernández-Lázaro, Fernando; Fukuzumi, Shunichi Resumen : Photoinduced electron-transfer dynamics of self-assembled donor–acceptor dyads formed by axial coordination of zinc naphthalocyanine, ZnNc, and perylenediimide (PDI) bearing either pyridine (py) or imidazole (im) coordinating ligands were investigated. The PDIim unit was functionalized with tertoctylphenoxy groups at the bay positions, which avoid aggregation providing solubility, to examine the effect of the bulky substituents at the bay positions on the rates of electron-transfer reactions. The combination between zinc naphthalocyanine and perylenediimide entities absorbs light over a wide region of the visible and near infrared (NIR) spectrum. The binding constants of the self-assembled ZnNc:PDIpy (1) and ZnNc:PDIim (2) in toluene were found to be 2.40 104 and 1.10 105 M 1, respectively, from the steady-state absorption and emission measurements, indicating formation of moderately stable complexes. The geometric and electronic calculations by using an ab initio B3LYP/6-311G method showed the majority of the highest occupied frontier molecular orbital (HOMO) on the zinc naphthalocyanine entity, while the lowest unoccupied molecular orbital (LUMO) was on the perylenediimide entities, suggesting that the charge-separated states of the supramolecular dyads are ZnNc +:PDI . The electrochemical results suggest the exothermic charge-separation process via the singlet states of both ZnNc and PDI entities in nonpolar toluene. Upon coordination of perylenediimide to ZnNc, the main quenching pathway involved charge separation via the singlet-excited states of ZnNc and PDIs. Clear evidence of the intramolecular electron transfer from the singlet-excited state of ZnNc to PDI within the supramolecular dyads in toluene was monitored by the femtosecond laser photolysis by observing the characteristic absorption band of the PDI radical anion (PDI ) and the ZnNc radical cation (ZnNc +) in the visible and NIR regions. The rate constants of charge-separation (kCS) processes of the self-assembled dyads 1 and 2 were determined to be 4.05 1010 and 1.20 109 s 1, respectively. The rate constant of charge recombination (kCR) and the lifetime of charge-separated states (tCS) of dyad 1 were determined to be 2.34 108 s 1 and 4.30 ns, respectively. Interestingly, a slower charge recombination (2.20 107 s 1) and a longer lifetime of the charge separated state (45 ns) were observed in dyad 2 in nonpolar toluene by utilizing the nanosecond transient measurements. The absorption in a wide section of the solar spectrum and the high charge-separation/charge-recombination ratio suggest the usefulness of the self-assembled zinc naphthalocyanine–perylenediimide dyads as good photosynthetic models.

2026-09-28T18:14:21Z Fukuzumi, Shunichi Ohkubo, Kei Ortiz, Javier Gutiérrez, Ana Mª Fernández-Lázaro, Fernando Sastre-Santos, Ángela https://hdl.handle.net/11000/40845 2026-09-28T17:48:47Z 2026-09-28T17:48:47Z

Título : Control of Photoinduced Electron Transfer in Zinc Phthalocyanine-Perylenediimide Dyad and Triad by the Magnesium Ion Autor : Fukuzumi, Shunichi; Ohkubo, Kei; Ortiz, Javier; Gutiérrez, Ana Mª; Fernández-Lázaro, Fernando; Sastre-Santos, Ángela Resumen : Photoexcitation of a zinc phthalocyanine-perylenediimide (ZnPc-PDI) dyad and a bis(zinc phthalocyanine)- perylenediimide [(ZnPc)2-PDI] triad results in formation of the triplet excited state of the PDI moiety without the fluorescence emission, whereas addition of Mg2+ ions to the dyad and triad results in formation of longlived charge-separated (CS) states (ZnPc•+-PDI•-/Mg2+ and (ZnPc)2 •+-PDI•-/Mg2+) in which PDI•- forms a complex with Mg2+. Formation of the CS states in the presence of Mg2+ was confirmed by appearance of the absorption bands due to ZnPc•+ and PDI•-/Mg2+ complex in the time-resolved transient absorption spectra of the dyad and triad. The one-electron reduction potential (Ered) of the PDI moiety in the presence of a metal ion is shifted to a positive direction due to the binding of Mg2+ to PDI•-, whereas the one-electron oxidation potential of the ZnPc moiety remains the same. The binding of Mg2+ to PDI•- was confirmed by the ESR spectrum, which is different from that of PDI•- without Mg2+. The energy of the CS state (ZnPc•+-PDI•-/ Mg2+) is determined to be 0.79 eV, which becomes lower that of the triplet excited state (ZnPc-3PDI*: 1.07 eV). This is the reason why the long-lived CS states were attained in the presence of Mg2+ instead of the triplet excited state of the PDI moiety.

2026-09-28T17:48:47Z Fukuzumi, Shunichi Ohkubo, Kei Ortiz, Javier Gutiérrez, Ana Mª Fernández-Lázaro, Fernando Sastre-Santos, Ángela https://hdl.handle.net/11000/40843 2026-09-28T17:34:05Z 2026-09-28T17:34:04Z

Título : Formation of a long-lived charge-separated state of a zinc phthalocyanine-perylenediimide dyad by complexation with magnesium ion Autor : Fukuzumi, Shunichi; Ohkubo, Kei; Ortiz, Javier; Gutiérrez, Ana Mª; Fernández-Lázaro, Fernando; Sastre-Santos, Ángela Resumen : Photoexcitation of a zinc phthalocyanine–perylenediimide (ZnPc–PDI) dyad affords the triplet excited state without the fluorescence emission, whereas addition of Mg2+ to the photoexcited ZnPc–PDI results in formation of a long-lived charge-separated state (ZnPc˙+–PDI˙−/Mg2+) in which PDI˙− forms a complex with Mg2+.

2026-09-28T17:34:04Z Foubelo, Francisco Gómez, C. Gutiérrez, Ana Mª Yus, Miguel https://hdl.handle.net/11000/40842 2026-09-28T17:07:00Z 2026-09-28T17:07:00Z

Título : Synthesis of substituted tetrahydroisoquinolines and benzo[d]azepines from phthalan or isochroman and N-silylaldimines Autor : Foubelo, Francisco; Gómez, C.; Gutiérrez, Ana Mª; Yus, Miguel Resumen : The 4,4′-di-tert-butylbiphenyl-catalyzed lithiation of phthalan (1a) and isochroman (1b) in THF at 0°C affords the corresponding functionalized benzyllithiums 2, which by reaction with N-silylaldimines yield, after acid-base work-up, the expected amino alcohols 3. Successive treatment of these amino alcohols with thionyl chloride and sodium hydroxide yields the corresponding substituted benzofused six- and seven-membered nitrogen-containing heterocycles 4.

2026-09-28T17:07:00Z Yus, Miguel Gutiérrez, Ana Mª Foubelo, Francisco https://hdl.handle.net/11000/40841 2026-09-28T16:28:06Z 2026-09-28T16:28:06Z

Título : Polylithiation of thioethers: a versatile route for polyanionic synthons Autor : Yus, Miguel; Gutiérrez, Ana Mª; Foubelo, Francisco Resumen : The successive reaction of phenyl vinyl thioether (1) with n-butyllithium and an electophile [E1=PhCHO, (CH2)4CO, (CH2)5CO] in THF at −78°C gives, after hydrolysis, the expected methylenic hydroxy thioethers (2). Deprotonation of 2 with n-butyllithium followed by a DTBB-catalysed lithiation and reaction with a second electrophile [E2=tBuCHO, PhCHO, Me2CO, (CH2)5CO], at −78°C, gives after hydrolysis the corresponding methylenic diols 3. The same diols can be prepared starting from 1 in a one-pot process without isolation of the hydroxy thioether 2. The same methodology was applied to the cyclopropyl phenyl thioether (4), cyclopropyl 1,3-diols 5 {E1=tBuCHO, PhCHO, [Me(CH2)4]2CO, (CH2)5CO, (CH2)7CO; E2=tBuCHO, Me2CO, (CH2)5CO} being isolated in moderate yields. The successive treatment of bis(phenylthio)methane (7) with: (a) n-butyllithium at 0°C, (b) a carbonyl compound [E1=tBuCHO, Me2CO, Et2CO, (CH2)5CO] at −40°C, (c) lithium and catalytic amount of DTBB (5%) and (d) a second carbonyl compound [E2=iPrCHO, tBuCHO, Me2CO, Et2CO, (CH2)5CO] both at −78°C leads, after hydrolysis, to the expected dihydroxy thioethers 8. When after step (d), a second DTBB-catalysed lithiation is performed at temperatures ranging between −78 and 20°C, the corresponding allylic alcohols 9 were isolated. Finally, treatment of alcohols 9 with a few drops of 6 M hydrochloric acid gives dienes 10 in almost quantitative yields.

2026-09-28T16:28:06Z Foubelo, Francisco Gutiérrez, Ana Mª Yus, Miguel https://hdl.handle.net/11000/40840 2026-09-28T16:05:42Z 2026-09-28T16:05:42Z

Título : Methane-derived polyanionic synthons from bis(phenylthio)methane Autor : Foubelo, Francisco; Gutiérrez, Ana Mª; Yus, Miguel Resumen : Successive treatment of bis(phenylthio)methane (1) with (a) n-butyllithium at 0°C, (b) a carbonyl compound [tBuCHO, Me2CO, Et2CO, (CH2)5CO] at −40°C, (c) lithium and a catalytic amount of DTBB (5%) and (d) a second carbonyl compound [iPrCHO, tBuCHO, Me2CO, Et2CO, (CH2)5CO], both at −78°C, leads, after hydrolysis, to the expected dihydroxy thioethers 5. When, after step (d), a second DTBB-catalysed lithiation is performed at temperatures ranging between −78 and 20°C, the corresponding allylic alcohols 7 are isolated. Finally, treatment of compounds 7 with 6 M hydrochloric acid give 1,3-dienes 10 in almost quantitative yield.

2026-09-28T16:05:42Z Foubelo, Francisco Gutiérrez, Ana Mª Yus, Miguel https://hdl.handle.net/11000/40839 2026-09-28T15:55:22Z 2026-09-28T15:55:22Z

Título : Phenyl vinyl thioether: A convenient source of the ethylene 1,1-dianion Autor : Foubelo, Francisco; Gutiérrez, Ana Mª; Yus, Miguel Resumen : The successive reaction of phenyl vinyl thioether (1) with n-butyllithium and an electrophile [El=PhCHO, (CH2)4CO, (CH2)5CO] in THF at −78°C gives, after hydrolysis, the expected methylenic hydroxy thioethers (2). Deprotonation of 2 with n-butyllithium followed by a DTBB-catalysed lithiation and reaction with a second electrophile [E2=1BuCHO, PhCHO, Me2CO, (CH2)5CO], also at −78°C, gives after hydrolysis the corresponding methylenic 1,3-diols 3. When carbon dioxide is used as the second electrophile, the expected methylenic hydroxy acid 3cd is isolated. The whole process can be performed in a one-pot manner without isolation of the intermediates 2.

2026-09-28T15:55:22Z Fernández-Martínez, Iván Espada, José P. Gonzálvez Maestre, María Teresa Morales Sabuco, Alexandra Orgilés, Mireia Muris, Peter https://hdl.handle.net/11000/40838 2026-09-28T10:07:01Z 2026-09-28T10:07:01Z

Título : Psychometric Evaluation of the Youth Anxiety Measure for DSM-5 (YAM-5) in a Community Sample of Spanish School-Aged Children Autor : Fernández-Martínez, Iván; Espada, José P.; Gonzálvez Maestre, María Teresa; Morales Sabuco, Alexandra; Orgilés, Mireia; Muris, Peter Resumen : The Youth Anxiety Measure for DSM-5 (YAM-5) was developed to assess symptoms of major anxiety disorders (Part I) and specific fears and phobias (Part II) in children and adolescents in accordance with current diagnostic criteria. Despite growing interest in the YAM-5, research has primarily focused on Part I, leaving Part II comparatively understudied, while evidence on the psychometric properties of both components in children from age eight onward remains limited. The present study examined the factorial structure and psychometric properties of both parts of the YAM-5 in a community sample of Spanish-speaking children aged 8 to 12 years. Participants were 515 children (M = 9.82, SD = 1.20) enrolled in primary education in Spain. Confirmatory factor analyses supported the original five-factor structure of both parts of the instrument. The YAM-5 total scale and the total scores of Parts I and II demonstrated good-to-excellent internal consistency, while most subscales showed acceptable-to-good reliability, with stronger internal consistency observed for Part I. Evidence of convergent, divergent, and discriminant validity was also found. These results provide further support for the YAM-5 as a suitable tool for assessing anxiety-related symptoms and facilitating their early identification among school-aged children in community settings.

2026-09-28T10:07:01Z Foubelo, Francisco Gutiérrez, Ana Mª Yus, Miguel https://hdl.handle.net/11000/40835 2026-09-28T07:15:52Z 2026-09-28T07:15:51Z

Título : Functionalized Organolithium Compounds by DTBB-Catalyzed Sulfur-Lithium Exchange Autor : Foubelo, Francisco; Gutiérrez, Ana Mª; Yus, Miguel Resumen : The successive reaction of β- or γ-hydroxy or amino phenyl thioethers (1, 4) with butyllithium and an excess of lithium powder in the presence of a catalytic amount of DTBB in THF at - 78 °C leads to the formation of the corresponding β-γ-functionalized organolithium compounds 2 or 5, respectively, which by treatment with different electrophiles [D2O, t-BuCHO, PhCHO, Me2CO, (CH2)4CO, (CH2)5CO] at temperatures ranging between - 78 °C and room temperature yields, after hydrolysis with water, the expected functionalized alcohols or amines 3 or 6, respectively, in a completely regioselective manner.

2026-09-28T07:15:51Z Foubelo, Francisco Gutiérrez, Ana Mª Yus, Miguel https://hdl.handle.net/11000/40834 2026-09-28T07:14:59Z 2026-09-28T07:14:59Z

Título : β-Functionalised Organolithium Compounds through a Sulfur-lithium Exchange Autor : Foubelo, Francisco; Gutiérrez, Ana Mª; Yus, Miguel Resumen : The successive reaction of different β-hydroxy or β-amino thioethers 1a-d with n-butyl-lithium and an excess of lithium powder and a catalytic amount of DTBB in THF at −78°C leads to the formation of the corresponding β-functionalised organolithium compounds 2a-d, which by reaction with several electrophiles [D2O, ButCHO, PhCHO, Me2CO, (CH2)5CO] at temperatures ranging between −78 and 20°C yields, after hydrolysis with water, the expected functionalised alcohols or amines 3aa-de in a regioselective manner.

2026-09-28T07:14:59Z