Metalloporphyrins in macromolecular chemistry

By systematic measurements we have evaluated a series of tetraphenyl metalloporphyrins and halogenated tetraphenyl metalloporphyrin derivatives for binding to ligands with oxygen containing functional groups, using methanol, acetic acid and acetone as examples. Experimental binding constants identified three metalloporphyrins with good binding to all three ligands: MgTPFPP, MgTPPBr8 and ZnTPPBr8 as well as a range of porphyrins binding to select ligands. Based on these results the optimal porphyrins can be selected for the desired binding interactions. We also show how to use DFT calculations to evaluate the potential binding between a metalloporphyrin and a ligand, which is deduced from free energies of binding ΔG, charge transfer ΔQ, and change of metal spin state. Computations on unsubstituted porphyrins in lieu of tetraphenyl porphyrin systems yield reliable predictions of binding interactions with good correlation to the corresponding experimental data. The calculations have also yielded interesting insights into the effect of halogenation in the β-position on the binding to ligands with oxygen containing functional groups.

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“…19 The insertion of metals into the porphyrins followed standard methods. 20,21 All metallopophyrins are shown in Scheme 1.…”

Section: Metalloporphyrinsmentioning

confidence: 99%

Design of oxophilic metalloporphyrins: an experimental and DFT study of methanol binding

2018

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“…Наиболее стабильным комплексом оказался MgAAAA, по-видимому, вследствие наличия атомов фтора, увеличивающих устойчивость к термическому разложению соединения. Наибольший тепловой эффект обнаружен для MgТАР(С 6 Н 5 ) 8 . В случае MgТАР(С 4 Н 8 ) 4 тепловой эффект (-1.5 кДж/г), как мы предполагаем на основе убыли массы, обусловлен процессом дегидрирования тетраметиленовых звеньев с образованием Mg-фталоцианина.…”

Section: термическая устойчивость Mg-азапорфириновunclassified

Stability of Magnesium(II) Azaporphyrins and Porphyrazines

Khelevina¹,

Ishutkina²,

Malyasova³

2013

MHC

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“…[1] The ability of metal porphyrinates to catalyze oxidation of organic and inorganic compounds is directly linked to the possibility of axial coordination of various substrates and on their activation. It should be noted that metal porphyrinate catalysts have found an important application in the catalytic oxidation of hydrogen sulfide, mercaptans and other RSH compounds with atmospheric oxygen.…”

Section: Introductionmentioning

confidence: 99%

“…[7] It stands to mention that the majority of studies covering the catalytic properties of porphyrins has been conducted on homogenous systems. [1,2,8,9] Therefore, extending the scope of the search for novel porphyrin catalysts unambiguously presents a significant scientific and practical interest.…”

Section: Introductionmentioning

confidence: 99%

“…An important matter, clearing of which would allow the synthesis of novel compounds with the desired set of properties, is finding correlations of adsorption and catalytic properties of porphyrins, in particular heterogenized on various carriers, with the structure of the macrocyclic ligand, the nature of the central metal atom [1,2,8,9] and the reaction medium. [10] Thus, particularly interesting are the porphyrins with pronounced electron-withdrawing properties that can act as electron scavengers and stabilize the central metal cation in lower oxidation states or unusual spin states.…”

Section: Introductionmentioning

confidence: 99%

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