Coordination Polymers Based on Aluminum(III) Porphyrins

Davidson, Gregory J. E.; Lane, Laura A.; Raithby, Paul R.; Warren, John E.; Robinson, Carol V.; Sanders, Jeremy K. M.

doi:10.1021/ic800587y

Cited by 33 publications

(20 citation statements)

References 16 publications

(15 reference statements)

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“…Generally, the presence of Al(III) metal in the porphyrin ring shifts the resonances of the porphyrin's protons to down-field accompanied by marginal changes in the pattern. In axially coordinated Al(III) porphyrin complexes, the signals of axial salicylate fragment protons are shifted to higher field in comparison to the signals of porphyrin protons and also in comparison to proton signals of free salicylic acid derivatives [23]. These positions of protons show that axial ligand is under the influence of -conjugated system of porphyrin macrocycle [24].…”

Section: Resultsmentioning

confidence: 93%

Electrochemical and Spectroscopic Characterization of Aluminium(III)-para-methyl-meso-tetraphenylporphyrin Complexes Containing Substituted Salicylates as Axial Ligands

Bajju

Deepmala

Anand

et al. 2013

International Journal of Electrochemistry

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A series of aluminium(III)-p-methyl-meso-tetraphenylporphyrin (p-CH3TPP-Al(III)) containing axially coordinated salicylate anion [p-CH3TPP-Al-X)], where X = salicylate (SA), 4-chlorosalicylate (4-CSA), 5-chlorosalicylate (5-CSA), 5-flourosalicylate (5-FSA), 4-aminosalicylate (4-ASA), 5-aminosalicylate (5-ASA), 5-nitrosalicylate (5-NSA), and 5-sulfosalicylate (5-SSA), have been synthesized and characterized by various spectroscopic techniques including ultraviolet-visible (UV-vis), infrared (IR) spectroscopy, proton nuclear magnetic resonance (1H NMR) spectroscopy,13C NMR, and elemental analysis. A detailed study of electrochemistry of all the synthesized compounds has been done to compare their oxidation and reduction mechanisms and to explain the effect of axial coordination on their redox properties.

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Section: Resultsmentioning

confidence: 93%

Electrochemical and Spectroscopic Characterization of Aluminium(III)-para-methyl-meso-tetraphenylporphyrin Complexes Containing Substituted Salicylates as Axial Ligands

Bajju

Deepmala

Anand

et al. 2013

International Journal of Electrochemistry

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“…Among the main group porphyrins, aluminum(III)porphyrins (AlPor) are unique, because the axial hydroxide of AlPor reacts with carboxylic acids to form covalent ester linkages while Lewis bases such as pyridine and imidazole form coordination bonds to the Al centre, which is a Lewis acid. [41][42][43][44][45][46] The combination of these properties makes AlPor a unique candidate for constructing 'axial-bonding' type multi-component D-AlPor-A systems. Over the last few years, we have reported a few novel AlPor based D-AlPor-A systems consisting of three-dimensional (3D) fullerene or two-dimensional (2D) naphthalenediimide as an electron acceptor and ferrocene, tetrathiafulvalene or phenothiazine entities as secondary electron donors.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast charge separation and charge stabilization in axially linked ‘tetrathiafulvalene–aluminum(iii) porphyrin–gold(iii) porphyrin’ reaction center mimics

Poddutoori

Lim

Vassiliev

et al. 2015

Phys. Chem. Chem. Phys.

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The axial bonding ability of aluminum(III) porphyrin (AlPor) has been exploited to synthesize the vertically linked dyad 'aluminum(III) porphyrin-gold(III) porphyrin' (AlPor-Ph-AuPor(+)) and the two corresponding self-assembled triads 'tetrathiafulvalene-aluminum(III) porphyrin-gold(III) porphyrin' (TTF-py→AlPor-Ph-AuPor(+) and TTF-Ph-py→AlPor-Ph-AuPor(+)). The unique topology of these triads provides an excellent opportunity to investigate the sequential electron transfer in the perpendicular direction to the AlPor plane where the AlPor acts as a photosensitizer and primary electron donor while the AuPor and TTF serve as an electron acceptor and donor, respectively. The ground state properties of the dyad and triad suggest that there are no direct intramolecular interactions between the oppositely disposed AuPor and TTF units of the triad. However, the NMR and UV-visible absorption studies of the dyad reveal intermolecular interactions in non-coordinating solvents due to the coordination of counterion PF6(-) to the Al center of AlPor. Steady-state and femtosecond transient absorption studies of the dyad show that the lowest excited singlet state of AlPor ((1)AlPor*) is strongly quenched by ultrafast electron transfer to AuPor(+) with a time constant of 3.16 ps. The resulting charge separated state (AlPor(+)˙-AuPor˙) decays to ground state biexponentially with time constants of 27.26 and 2557 ps. Analogously, upon photo-excitation the triads also produce the same primary radical pair (AlPor(+)˙-AuPor˙). However, the formed radical pair is further involved in a rapid hole transfer from AlPor(+)˙ to TTF to form a stable final radical pair TTF(+)˙-AlPor-AuPor˙. The lifetime of the charge separated state exhibits an increase from 27.26 ps in AlPor-Ph-AuPor to 1393 ps in TTF-py→AlPor-Ph-AuPor(+) and 1484 ps in TTF-Ph-py→AlPor-Ph-AuPor(+). These results reveal successful charge stabilization in the self-assembled supramolecular reaction center mimics constructed via the axial linkage strategy.

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“…Porphyrins are an ideal choice for this purpose due to the facile tunability of their electronic properties through modification of the attached substituents or through metallation of the porphyrin macrocycle, 24 and they can easily be attached to a variety of scaffolds. [25][26][27][28][29][30][31][32] Other groups have used porphyrin-DNA constructs to create DNA bundles and tubes, 33,34 to form porphyrin dimers through hybridisation, 35 or as chiral markers for the analysis of DNA structure by CD spectroscopy. 36,37 Previous research in our group has focused on tetraphenyl porphyrin (TPP, 1) 38 or diphenyl porphyrin (DPP) 39 moieties connected via a rigid acetylene linker (Fig.…”

Section: Introductionmentioning

confidence: 99%

Introducing structural flexibility into porphyrin–DNA zipper arrays

et al. 2011

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A more flexible nucleotide building block for the synthesis of new DNA based porphyrin-zipper arrays is described. Changing the rigid acetylene linker between the porphyrin substituent and the 2'-deoxyuridine to a more flexible propargyl amide containing linkage leads in part to an increased duplex stability. The CD spectra reveal different electronic interactions between the porphyrins depending on the type of linker used. Molecular modelling suggests large variation of the relative orientation of the porphyrins within the major groove of the DNA. The porphyrins can be metallated post-synthetically with different metals as shown with zinc, cobalt and copper. The spectroscopic features do not alter drastically upon metallation apart from the CD spectra, and the stability of the metal complex is highly dependent on the nature of the metal. As shown by CD spectroscopy, the zinc porphyrin is rapidly demetallated at high temperatures. Globular structure determination using SAXS indicates that a molecular assembly comprised of a two to four helical bundle dominates in solution at higher concentrations (≥50 μM) which is not observed by spectroscopy at lower concentrations (≤1 μM).

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Coordination Polymers Based on Aluminum(III) Porphyrins

Cited by 33 publications

References 16 publications

Electrochemical and Spectroscopic Characterization of Aluminium(III)-para-methyl-meso-tetraphenylporphyrin Complexes Containing Substituted Salicylates as Axial Ligands

Electrochemical and Spectroscopic Characterization of Aluminium(III)-para-methyl-meso-tetraphenylporphyrin Complexes Containing Substituted Salicylates as Axial Ligands

Ultrafast charge separation and charge stabilization in axially linked ‘tetrathiafulvalene–aluminum(iii) porphyrin–gold(iii) porphyrin’ reaction center mimics

Introducing structural flexibility into porphyrin–DNA zipper arrays

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