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Projeto de investigação
Associated Laboratory for Green Chemistry - Clean Technologies and Processes
Financiador
Autores
Publicações
Functional alginate aerogels as green catalytic platform for CO₂-to-syngas conversion [Resumo]
Publication . Messias, Sofia; Paninho, A. B.; Vieira, G.; Souza, A.; Rangel, Carmen M.; Nunes, Daniela; Martins, Rodrigo; Mendes, Manuel Joao; Machado, Ana
Enhancing Proton Conductivity of SPEEK Based Membranes by Incorporation Graphene Oxide / Bisphosphonic acid dopant [Resumo]
Publication . Teixeira, Fatima; Teixeira, António Paulo Silva; Rangel, Carmen M.
ABSTRACT: The most commercially successful membrane for applications in fuel cell and electrolyzers, perfluorinated sulfonic NafionR, exhibits relevant performance limitations due to its dependence on water content with consequent proton mobility restrictions, environmental concerns and very high cost. Poly(etheretherketone) (SPEEK) polymer appears as a versatile non-fluorinated alternative for a low-cost and a more environmentally friendly membrane. Our previous studies showed that the incorporation of biphosphonic acid dopants (BPs) into the mentioned polymeric matrices, improves membrane proton conduction and durability1-5. In this work, we prepared and evaluated new doped SPEEK membranes using graphene oxide (GO) with bisphosphonic acid functionalities as dopant (GOBP), anticipating superior membranes properties, including proton conductivity.
Green Catalytic Transformation of CO₂ to Syngas Using Aerogels [Resumo]
Publication . Paninho, A. B.; Messias, Sofia; Fernandes, I.; Rangel, Carmen M.; Nunes, A. V. M.; Branco, Luis; Martins, Rodrigo; Mendes, Manuel Joao; Machado, Ana
Cyclopentadienyl vs indenyl control of thermal/photoactivated CO release in cationic molybdenum(II) dicarbonyl-ethylenediamine complexes
Publication . Bruno, Sofia M.; Calhau, Isabel B.; Dias, Tiago M.; Santos, Adriana; Silva, Luis Cunha; Nolasco, Mariela M.; Goncalves, Isabel S.; Pillinger, Martyn
ABSTRACT: Molybdenum half-sandwich carbonyl complexes continue to attract attention as potential anticancer agents and prodrugs for therapeutic use of carbon monoxide. Building on the known bioactivity and hydrolytic stability of cyclopentadienyl-based Mo fragments, we report the synthesis, structural characterization, and solution behavior of two cationic half-sandwich complexes, [(eta 5-Cp)Mo(CO)2(en)][BF4] (3) and [(eta 5-Ind)Mo(CO)2(en)][BF4] (4) (Cp = cyclopentadienyl, Ind = indenyl, en = ethylenediamine). Complex 3 is described here for the first time, while 4 was structurally characterized by single-crystal X-ray diffraction, revealing a distorted square-pyramidal geometry with cis-CO ligands and a chelating en ligand positioned beneath the indenyl ring. Both compounds are air-stable in the solid state and exhibit enhanced solubility in polar media due to their ionic nature. UV-vis stability studies under simulated physiological conditions (PBS, pH 7.4, 37 degrees C) show gradual decomposition of both complexes, accelerated by visible-light irradiation and/or the presence of air. CO-release behavior was quantified using the myoglobin assay: the allyl precursors [(eta 5-Cp')Mo(eta 3-C3H5)(CO)2] were inert, whereas complexes 3 and 4 released CO slowly, with 4 exhibiting significantly faster thermal CO liberation (t1/2 approximate to 129 min; 0.74 equiv. CO after 6 h). Complex 3 showed minimal thermal CO release but underwent enhanced and sustained photodecarbonylation under visible-light irradiation, enabling controlled CO delivery. These results identify 3 and 4 as rare examples of Mo-based CO-releasing molecules capable of slow, tunable CO release under biologically relevant conditions, with 3 displaying light-responsive behavior and 4 functioning as a spontaneous thermal CO donor.
A molecular 'LEGO®' approach to high-spin triangular {MnIIILn2} clusters from {MnIII} and {Ln2} metalloligands
Publication . Pantelis, Konstantinos N.; Cunha-Silva, Luís; Saber, Mohamed R.; Dunbar, Kim R.; Alexandropoulos, Dimitris I.; Stamatatos, Theocharis
ABSTRACT: A stepwise "LEGO (R)-brick" strategy has been employed for the targeted assembly of rare low-nuclearity MnIII/LnIII clusters from preformed molecular building units. The mononuclear MnIII metalloligand (Pr2NH2)[MnIII(sacb)2] (1; sacbH2 = N-salicylidene-2-amino-5-chlorobenzoic acid) was combined with newly isolated dinuclear lanthanide complexes [Ln2(sacb)(sacbH)3L(MeOH)] [LnIII = Dy (2), Gd (3); L- = 2-amino-5-chlorobenzoate], affording the trinuclear heterometallic compounds [MnIIILn2(sacb)3(sacbH)2L] [LnIII = Dy (4), Gd (5)]. Single-crystal X-ray diffraction studies revealed that 4 and 5 possess triangular {MnIIILn2(mu-O2CR)3}6+ cores, representing the first structurally characterized triangular {MnIIILn2} complexes and rare examples of triangular {MLn2} (M = any 3d-metal ion) clusters. Magnetic studies have demonstrated that the MnIII-free {Dy2} precursor 2 displays weak field-induced slow relaxation of magnetization, whereas incorporation of the Jahn-Teller active MnIII ion leads to ferromagnetically coupled {MnIIILn2} species. In particular, the {MnIIIGd2} analogue 5 exhibits a high-spin ground state of S = 9, with weak ferromagnetic MnIII & ctdot;GdIII and GdIII & ctdot;GdIII exchange interactions. Although no slow magnetic relaxation was observed for the trinuclear complexes, the results demonstrate that controlled integration of a MnIII metalloligand can promote ferromagnetic exchange in preassembled {Ln2} units and provide a direct route to structurally defined high-spin 3d/4f triangles.
Unidades organizacionais
Descrição
Palavras-chave
Sustainable Chemistry and Clean Processes,Food Science and Technology,Chemistry to Health & Wellbeing,Cultural Heritage, Exact and natural sciences
Contribuidores
Financiadores
Entidade financiadora
Fundação para a Ciência e a Tecnologia, I.P.
Programa de financiamento
Concurso para Atribuição do Estatuto e Financiamento de Laboratórios Associados (LA)
Número da atribuição
LA/P/0008/2020