Properties of porphyrin dimers, formed by pairing cationic and anionic porphyrins

Ojadi, Emmanuel; Selzer, Russell; Linschitz, Henry

doi:10.1021/ja00311a105

Cited by 113 publications

(54 citation statements)

References 2 publications

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“…This driving force toward association can be enhanced by electrostatic interactions when oppositely charged species are put together [34]. In this case, the formation of stacked ion pairs is strongly favored, as previously reported for [ZnTPyP(Ru(bipy) 2 Cl] 4 ) 4 and [M-TPPS] 4À , leading to the precipitation of an unsoluble, layered material from methanolic solution [35].…”

Section: Stacked Ion Pairssupporting

confidence: 52%

Synthesis and Characterization of a Novel Dodecanuclear Porphyrin Ruthenium Cluster

Toma

Araki

Silva

1998

Monatshefte fuer Chemie

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A new symmetric dodecanuclear complex constituted by a 5,10,15,20-tetra pyridyl porphyrin centre coordinated to four triangular "-oxo-ruthenium acetate clusters, [Ru 3 O (Ac) 6 (py) 2 ] ( py pyridine), is reported. Its electrochemical and spectroelectrochemical behaviour involves ®ve accessible oxidation states of the cluster unities, in addition to the porphyrin oxidation and reduction waves, in the range of À1.5 to 2.4 V. The cluster porphyrin species associates very strongly with tetrasulfonate phthalocyaninatecopper (II), forming electrostatically assembled stacked compounds both in dimethylsulfoxide solution and in the solid state.

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Section: Stacked Ion Pairssupporting

confidence: 52%

Synthesis and Characterization of a Novel Dodecanuclear Porphyrin Ruthenium Cluster

Toma

Araki

Silva

1998

Monatshefte fuer Chemie

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“…This metalloporphyrin (ZnTPP) is of particular interest as its EPR triplet spectrum, i) does not always reflect the axial symmetry (D4h) of this compound in the gas phase [84]; ii) reveals no transient behavior (ESP) under conventional light modulation detection. It should be noted however, that its water soluble porphyrin analog does exhibit an ESP effect [85].…”

Section: Spatial Distribution Functionmentioning

confidence: 99%

Spin polarized triplets oriented in liquid crystals

Levanon

1987

Reviews of Chemical Intermediates

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“…These molecules have been joined through covalent alkyl chains, 5 peptide bond, hydrogen bond, 6 rigid spacers, 7 self-assembled via metal-ligands, 8 or more recently, through ion pairing formed by association of molecules grafted with oppositely charged substituents. 9,10 Synthetic macrocycles such as porphyrins, and structurally similar phthalocyanines share many of the characteristics of the naturally occurring porphyrin-like systems. Spontaneous aggregation between porphyrins and phthalocyanines bearing charged peripheral substituents occurs in solution, and thus, these molecules have been employed to study face-to-face heterodimer bound electrostatically.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of new cationic metalloporphyrins and heterodimer formation with anionic metallophthalocyanines

Ribeiro

Azzellini

2003

J. Braz. Chem. Soc.

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Existe grande interesse no estudo de heterodímeros constituídos por metaloporfirinas e ftalocianinas de carga oposta, uma vez que estes sistemas são modelos do special pair da fotossíntese e dispositivos moleculares promissores para a transferência de elétrons unidirecional. Neste trabalho foram sintetizadas novas metaloporfirinas catiônicas, e investigada a formação de heteroagregados com metaloftalocianinas aniônicas em DMSO. Estes novos derivados porfirínicos catiônicos apresentam grupos benzílicos ligados aos nitrogênios piridínicos da tetra-(piridil)porfirina (H 2 TPyP), resultando em compostos que são mais hidrofóbicos e que apresentam sistemas π adicionais em relação aos ligantes tetra-(metilpiridínio)porfirina (H 2 TMPyP) e tetra-(trimetilaminofenil)porfirina (H 2 TAPP). Observou-se que a estequiometria dos agregados formados e os valores de constante de associação entre as porfirinas catiônicas e as ftalocianinas aniônicas são dependentes do metal coordenado a ambos os macrociclos. As Zn(II)porfirinas formam em solução preferencialmente o agregado de estequiometria 1:1 (porfirina:ftalocianina) no meio reacional, enquanto que no caso das Pd(II)porfirinas pode ocorrer a formação de agregados 1:1 ou 1:2 (porfirina:ftalocianina). Os valores de K PI , por sua vez, são sempre maiores para os agregados formados com as ftalocianinas de Cu(II), sendo este comportamento relacionado com a menor distorção para fora do plano da ligação Cu-N comparada com a ligação Ni-N em decorrência da ligação axial de uma molécula de DMSO ao íon metálico coordenado à ftalocianina. Os valores de K PI também são menores para os heterodímeros formados com as porfirinas que apresentam os meso-susbtituintes benzílicos mais volumosos, em função da disposição angular dos mesmos em relação ao plano do anel porfirínico que provoca um maior impedimento estérico. Estes resultados demonstram que a associação entre macrociclos tetrapirrólicos pode ser controlada através de vários fatores estruturais. Estes fatores também podem conduzir a diferentes propriedades fotofísicas destes heteroagregados; estudos neste sentido estão em andamento.There is great interest in the investigation of heterodimers formed by metalloporphyrins and metallophthalocyanines grafted with oppositely charged substituents, since these systems are models of the photosynthetic special pair and promising unidirectional electron transfer molecular devices. In the present study new cationic metalloporphyrin derivatives were synthesized and their association with anionic metallophthalocyanines forming heteroaggregates, investigated. These new cationic porphyrins derivatives show benzylic groups bound to the pyridyl nitrogen atoms of tetra-(pyridyl)porphyrin (TPyP), resulting in additional π systems and more hydrophobic compounds if compared with tetra-(methylpiridinium)porphyrin (H 2 TMPyP) and tetra-(trimethylaminophenyl)porphyrin (H 2 TAPP) ligands. It could be observed that both stoichiometry and association constants between cationic porphyrins and anionic phthalocyanines ...

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Properties of porphyrin dimers, formed by pairing cationic and anionic porphyrins

Cited by 113 publications

References 2 publications

Synthesis and Characterization of a Novel Dodecanuclear Porphyrin Ruthenium Cluster

Synthesis and Characterization of a Novel Dodecanuclear Porphyrin Ruthenium Cluster

Spin polarized triplets oriented in liquid crystals

Synthesis of new cationic metalloporphyrins and heterodimer formation with anionic metallophthalocyanines

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