Photocatalytic reactions of a nickel(<scp>ii</scp>) annulene complex incorporated in polymeric structures

Estiú, Guillermina; Ferraudi, G.; Lappin, A. Graham; Ruiz, Gustavo Miguel; Vericat, Carolina; Costamagna, J.; Villagrán, Manuel Aguilar

doi:10.1039/c4ra08177c

Cited by 3 publications

(8 citation statements)

References 40 publications

(42 reference statements)

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“…The redox reaction of CS with mannitol bares a strong resemblance with the reduction of CS by trimethylamine, with a mechanism involving either an electron transfer or a proton-coupled electron transfer, eq. 7 [1,10]. Very similar values of k r were calculated for the [Ni I (tmdbTAA-CO---)]decay in mannitol and sucrose containing solutions, Table I.…”

Section: Resultssupporting

confidence: 63%

“…The work expands knowledge of the range of sacrificial reductants useful with these polymeric reagents and where poly([Ni II (tmdbTAA)]) has been employed in the photoinduced reduction of CO 2 to CO. 1 In prior work, inorganic S(IV) was used as the sacrificial reagent, but the findings of this work suggest that agricultural wastes rich in carbohydrates might also be used.…”

Section: Discussionmentioning

confidence: 87%

“…In the dAMP case, the desoxyribose will be first oxidized and will transfer the oxidation to the adenine in a subsequent step. luminescence [1]. Interestingly, under these energetic restrictions there is a strong resemblance between the dAMP quenching of the respective poly([Ni II (tmdbTAA)]) and 9-aminoacridine luminescence [13].…”

Section: Resultsmentioning

confidence: 99%

“…The extension of the redox photochemistry of metal macrocyclic complexes into the polymeric realm affords a number of interesting possibilities for cooperative interactions and unique chemistry. [1][2][3][4][5] excited to their short lived singlet and triplet excited states, eq. 1, 2, which are then converted to phthalocyanine-centered radicals in processes occurring in microseconds, eq.…”

mentioning

confidence: 99%

“…4, which subsequently form charge-separated macrocyclic pendants, CS, with a lifetime, τ ~30 ns, eq. 5 [1].…”

mentioning

confidence: 99%

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Photoinduced oxidation reactions of the pendent macrocyclic complexes: Al(III) phthalocyanine and Ni(II) annulene mechanistic considerations

et al. 2016

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The goal of the work was to expand the understanding of the photoinduced redox reactions of the Al(III) sulfonated phthalocyanine, HOAl III tspc, and Ni(II) tertramethyldibenzotetraazaannnulene, [Ni II (tmdbTAA)], as components of polymeric structures in which poly(ethyleneimino) and poly(isobutyl-alt-maleate) are the respective backbones of poly(HOAl III tspc) and poly([Ni II (tmdbTAA)]). Saccharide and flavonoid glycosides form adducts that quench the photo-generated oxidizing radicals in the case of poly(HOAl III tspc) with rate constants ≈ 1 x 10 4 s -1 , largely independent of reductant structure. The charge-separated intermediate, CS, in the case of poly([Ni II (tmdbTAA)]) shows greater reactivity with the saccharides and flavonoid glycosides, particularly with the flavonoid glycoside rutin where the rate constant is 2.7 x 10 6 s -1 . While phthalocyanine-centered radicals in poly(HOAl III tspc) were

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Section: Resultssupporting

confidence: 63%

Section: Discussionmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

“…4, which subsequently form charge-separated macrocyclic pendants, CS, with a lifetime, τ ~30 ns, eq. 5 [1].…”

mentioning

confidence: 99%

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Photoinduced oxidation reactions of the pendent macrocyclic complexes: Al(III) phthalocyanine and Ni(II) annulene mechanistic considerations

et al. 2016

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Multichromophore arrays of dibenzotetraaza[14]annulene: a promising platform for bioorganic chemistry

Zwoliński

Eilmes

2018

Org. Biomol. Chem.

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The first series of discrete multichromophore arrays of dibenzotetraaza[14]annulene (DBTAA), containing flexible bridges, have been synthesized in 40-46% isolated yields. The key asymmetrical intermediates, carrying two distinctly addressable functionalities (ROH vs. ROCH2-C[triple bond, length as m-dash]C-H and R(CH2)nBr vs. ROCH2-C[triple bond, length as m-dash]C-H) at the macrocycle periphery, were synthesized in moderate to high (30-78%) isolated yields. Facile synthetic protocols developed for the synthesis of discrete DBTAA arrays offer several advantages such as operational simplicity and easy post-synthetic workup that overcome the need for laborious chromatographic purification. All new compounds were characterized by microanalysis, mass spectrometry, UV-Vis, FTIR-ATR, and 1H and 13C NMR spectroscopy. Structural features were briefly discussed with emphasis on several potential applications.

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Review: Properties and chemical reactivity of metallo phthalocyanine and tetramethylbenzoannulene complexes grafted into a polymer backbone

Ferraudi

Lappin

2014

Journal of Coordination Chemistry

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The properties of coordination complexes grafted to a polymer backbone are reviewed in this article. The focus is on complexes of phthalocyanine and tetraazaannulene (5,7,12,14-tetramethyldibenzo[b,i] [1,4,8,11]tetraazacyclotetradecine, also abbreviated tmdbztaa) with various transition metal ions and Al(III). In addition to the morphological characteristics of the materials, their thermal and photochemical reactions are reviewed. Processes such as catalysis of the lignin degrading process and the reduction of CO 2 are presented as examples of these materials potential applications. tmdbztaa = 5,7,12,14-tetramethyldibenzo[b,i]-1,4,8,11-tetraaza[14]annulene tspc = phthalocyaninetetrasulfonate trspc = phthalocyaninetrisulfonate pc = phthalocyanine TEM = transmission electron microscope AFM = atomic force microscope eaq = solvated electron in aqueous solutions esol = solvated electron in organic medium k ob = experimentally determined pseudo-first order rate constant k/ε = ratio of the second order rate constant to the extinction coefficient at the wavelength of the probe Downloaded by [New York University] at 03:51 14 October 2014 2 λ ex = wavelength of the light used for the irradiation of the light absorbing compound (HOMO-6) 1 (LUMO) 1 -dd 3 ππ* = triplet excited state resulting in an electronic transition between low energy π and higher energy π* orbitals 3 LF = triplet metal-centered excited state Abbreviated names of the polymers with their corresponding structures can be seen in figure 1. Abbreviations used in the text IntroductionThe extensive and diverse chemistry of transition metal coordination complexes can be modified when the complexes are grafted into a polymer backbone. This extends the chemistry to different conditions that can be used for practical applications [1][2][3][4][5][6][7][8][9]. There has been an increasing interest in the design, synthesis and use of diverse macrocyclic receptors capable of selective recognition of metal ions, anions and neutral molecules [10 -24]. Such macrocyclic receptors are readily incorporated in polymer matrices. In this role, polyazamacrocycles have been extensively studied [11][12][13][14][15][16] because they are able to coordinate divalent metal cations, such as Ni 2+ or Cu 2+ , by displacing the amide protons. The complexes have many applications in catalysis [23], molecular machines, oxygen uptake [18, 19], medicine [18], as antiviral agents [25][26][27], and can also be studied as biological models for metalloproteins [28] in a polymeric environment. For example, the structural features of the macrocycles and the unique radiophysical properties of copper radioisotopes have led to their potential usefulness in diagnostic and/or therapeutic applications [29].Among the metal complexes that can be grafted into a polymer, the annuleno and phthalocyanine ligands are of a particular interest because they can catalyze thermal and photochemical reactions. In addition to other applications, these complexes are competent in the photoinduced oxidative degradation of...

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Photocatalytic reactions of a nickel(ii) annulene complex incorporated in polymeric structures

Abstract: A study of the structural and chemical processes of a new polymeric photocatalyst containing a Ni(ii) macrocyclic complex and its application to the solar reduction of CO2 in aqueous homogeneous solution.

Cited by 3 publications

References 40 publications

Photoinduced oxidation reactions of the pendent macrocyclic complexes: Al(III) phthalocyanine and Ni(II) annulene mechanistic considerations

Photoinduced oxidation reactions of the pendent macrocyclic complexes: Al(III) phthalocyanine and Ni(II) annulene mechanistic considerations

Multichromophore arrays of dibenzotetraaza[14]annulene: a promising platform for bioorganic chemistry

Review: Properties and chemical reactivity of metallo phthalocyanine and tetramethylbenzoannulene complexes grafted into a polymer backbone

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