Complex formation between porphyrins and metal ions

Burnham, Bruce F.; Zuckerman, J. J.

doi:10.1021/ja00709a019

Cited by 44 publications

(14 citation statements)

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“…31 After this report, the reports on the detection of the SAT complex have been very limited, only in peculiar systems. [32][33][34][35] We think that a crucial point to form the SAT complex is to guarantee the thermodynamic and kinetic retardation of the dissociation of protons on the pyrrole rings in the SAT complex. Therefore, we must select solvents with a very low Brønsted basicity; water as a solvent is not adequate.…”

Section: Kinetics and Mechanism For Sitting-atop (Sat) Complex Formationmentioning

confidence: 99%

“…Because the two pyrrolenine groups can potentially bind to the metal ion, the overall metalation reaction will consist of at least two steps, i.e., the coordination step of two pyrrolenine nitrogens to form an intermediate, the so-called sitting-atop (SAT) complex, M(H2por) n+ , 31 in which two protons on the pyrrole nitrogens still remain, [32][33][34][35] and the deprotonation step of the SAT complex to form the metalloporphyrin, as shown by Eqs. (2) and (3), respectively.…”

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confidence: 99%

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Dynamic Study of Metal-Ion Incorporation into Porphyrins Based on the Dynamic Characterization of Metal Ions and on Sitting-Atop Complex Formation

2001

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The metalloporphyrin formation reaction is one of the important processes from both analytical and bioinorganic points of view.The large molar absorption coefficient and very high stability of the metalloporphyrins are very useful for the highly sensitive analysis of trace amounts of metal ions, and the size selectivity of the porphyrins is valuable for the separation of various kinds of metal ions. 1-7 A variety of metalloporphyrin formation rates are also applicable for the kinetic analysis of metal ions. We succeeded in the detection of the sitting-atop (SAT) copper(II) complex of TPP (5,10,15,20-tetraphenylporphyrin) in acetonitrile (AN) as a solvent with a very low Brønsted basicity, where two pyrrolenine nitrogens in the Cu(II)-SAT complex coordinate to the metal ion and two protons still remain on the pyrrole nitrogens. The structure parameters around the copper(II) ion in the Cu(II)-SAT complex, as determined by a fluorescent EXAFS method, suggest an axially elongated and equatorially distorted six-coordinate geometry. We measured the rates of the formation reaction of the SAT complexes for a series of transition metal(II) ions in AN using the stopped-flow technique. We propose the mechanism where there is a rapid deformation equilibrium of the porphyrin ring prior to the rate-determining step of the bond rupture of a coordinated solvent molecule on the metal(II) ion. Furthermore, we measured the rates of the deprotonation reaction of the Cu(II)-SAT complex by some Brønsted bases and indicated that the rate-determining step is the attack of the base on the proton of the pyrrole nitrogen in the SAT complex. Finally, a unified mechanism relevant to the porphyrin metalation mechanism has been proposed.

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Section: Kinetics and Mechanism For Sitting-atop (Sat) Complex Formationmentioning

confidence: 99%

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confidence: 99%

Dynamic Study of Metal-Ion Incorporation into Porphyrins Based on the Dynamic Characterization of Metal Ions and on Sitting-Atop Complex Formation

2001

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“…The synthesi s of Sn and Fe cyto chro m es c (50% enri chm ent i n 5 7 Fe, na tura l abunda nce 1 1 9 Sn) has b een do ne accordi ng to V anderko o i [6] and Burnha m and Zuckerm an [7] wi th some m odi Ùcati ons [8]. The puri ty of the com p ounds was checked by the opti cal Ûuorescence m etho d.…”

Section: M At Er I a L S An D M Et H O D Smentioning

confidence: 99%

Application of Mössbauer Spectroscopy in Study of Selected Biochemical Processes

Burda

Staněk

2003

Acta Phys. Pol. A

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“…Researchers investigating OLEDs have studies on determining alternative molecules that are superior to these compounds. [65,66] Since both porphyrin and porphyrin complexes are electron-rich molecules, they are expected to be good candidates for OLED materials (Scheme 1). [49][50][51][52] Recently, the scientists have focused on improving the materials having a high charge transfer rate and exhibiting strong emission in the visible region to increase the performance of OLEDs.…”

Section: Introductionmentioning

confidence: 99%

“…[18,19] In addition to these layers, there are electron injection layer (EIL), [21,22] electron blocking layer (EBL), [23,24] hole injection layer (HIL), [25,26] and hole blocking layer (HBL) [27,28] between cathode and anode. [65,66] Since both porphyrin and porphyrin complexes are electron-rich molecules, they are expected to be good candidates for OLED materials (Scheme 1). [29][30][31][32][33] N,N 0 -diphenyl-N,N 0 -bis (3-methyl phenyl)-(1,10-biphenyl)-4,4 0 -diamine (TPD) [34][35][36] and tris(8-hydroxyquinolinato)aluminum(III) (Alq3) [37][38][39] are a typical HTL and a ETL material, respectively.…”

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Electronic, optical, and charge transfer properties of porphyrin and metallated porphyrins in different media

Üngördü

2019

Int J of Quantum Chemistry

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Porphyrin and M-Porphyrin (M = Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ) complexes were designed to examine their organic light-emitting diode (OLED) properties. All calculations were performed in different media, which are gas, benzene, DMSO, and water phases. The calculations of both porphyrin and its metal complexes as a monomer form were performed at B3LYP/6-31G(d) level by using the Gaussian 16 and GaussView 6 package programs. On the other hand, emission calculations for the monomer form and dimer form computations of the studied compounds were carried out at PBE0/TZP and B3LYP/TZP levels, respectively, by using Amsterdam density functional (ADF) 2019 package program. The OLED tensors of the mentioned molecules, which are emission energies, reorganization energies (λ e and λ h ), the ionization potentials and the electron affinities (adiabatic and vertical), the effective transfer integrals (V e and V h ), and the charge transfer rates (W e and W h ), were calculated to evaluate the OLED behaviors and determine the best OLED structure. K E Y W O R D Scharge transfer rate, OLED material, porphyrin, reorganization energy, transfer integral | INTRODUCTIONThe improvement of organic light-emitting diodes (OLEDs) including π-conjugated systems has been of interest over the past decade due to their economical and efficient applications in next-generation display technology and lighting field. [1][2][3][4][5][6][7][8][9] These systems can consist of metal-free or metallated compounds. [10][11][12][13][14][15][16][17] Fundamentally, used compounds in OLED structure have been classified as electron-transporting layers (ETL), [18][19][20] hole-transporting layers (HTL), [18,19] and emissive layers (EL). [18,19] In addition to these layers, there are electron injection layer (EIL), [21,22] electron blocking layer (EBL), [23,24] hole injection layer (HIL), [25,26] and hole blocking layer (HBL) [27,28] between cathode and anode. EL materials are found between ETL and HTL materials and emit light from red to blue depending on the wavelength of the emission. [29][30][31][32][33] N,N 0 -diphenyl-N,N 0 -bis (3-methyl phenyl)-(1,10-biphenyl)-4,4 0 -diamine (TPD) [34][35][36] and tris(8-hydroxyquinolinato)aluminum(III) (Alq3) [37][38][39] are a typical HTL and a ETL material, respectively. While TPD is metal-free molecules, Alq3 is metallated organic molecules. Researchers investigating OLEDs have studies on determining alternative molecules that are superior to these compounds. [40][41][42][43][44][45][46][47][48] Additionally, color properties of emitter materials in EL layer have been studied. [49][50][51][52] Recently, the scientists have focused on improving the materials having a high charge transfer rate and exhibiting strong emission in the visible region to increase the performance of OLEDs. [53][54][55][56][57][58][59] For this purpose, they have modified the compounds via using the metal or substituent. [15,[60][61][62][63][64] Porphyrin is a planar, aromatic macrocyclic ring consisting of four pyrrole units havin...

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Complex formation between porphyrins and metal ions

Cited by 44 publications

References 1 publication

Dynamic Study of Metal-Ion Incorporation into Porphyrins Based on the Dynamic Characterization of Metal Ions and on Sitting-Atop Complex Formation

Dynamic Study of Metal-Ion Incorporation into Porphyrins Based on the Dynamic Characterization of Metal Ions and on Sitting-Atop Complex Formation

Application of Mössbauer Spectroscopy in Study of Selected Biochemical Processes

Electronic, optical, and charge transfer properties of porphyrin and metallated porphyrins in different media

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