A Lipophilic Hexaporphyrin Assembly Supported on a Stannoxane Core

Chandrasekhar, Vadapalli; Nagendran, Selvarajan; Azhakar, Ramachandran; Kumar, Murugaeson R.; Srinivasan, A.; Ray, Kallol; Chandrashekar, Tavarekere K.; Madhavaiah, C.; Verma, Sandeep; Priyakumar, U. Deva; Sastry, G. Narahari

doi:10.1021/ja043748g

Cited by 53 publications

(34 citation statements)

References 29 publications

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“…In this context, we recently reported the utility of a hexacopper-metalated porphyrin-linked stannoxane cage showing selective DNA-cleavage activity, without the addition of any external cooxidant. [19] These efforts led us to evaluate the viability of less-wellexplored corrole macrocycles for their DNA-scission activity. The Cu II complexes 7 a and 9 a were initially probed for the photocleavage of supercoiled DNA.…”

Section: Epr and Magnetic Propertiesmentioning

confidence: 99%

meso–meso‐Linked Corrole Dimers with Modified Cores: Synthesis, Characterization, and Properties

Sankar

Rath

Prabhuraja

et al. 2006

Chemistry A European J

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The synthesis and characterization of the first examples of core‐modified corrole dimers linked through the meso positions are described. The dimers are obtained by a simple AgI‐ or FeIII‐catalyzed coupling reaction in near‐quantitative yields. The corroles obtained are metalated with metal ions, such as CuII and NiII. The electronic‐absorption spectral studies reveal weak electronic interaction between the two subunits and the exciton coupling observed for the free‐base corrole dimer (1717 cm−1) is lower than that for the corresponding protonated derivative (4081 cm−1). The solution‐state structure derived from 1H and two‐dimensional NMR spectral studies reveals a noncoplanar arrangement of two corrole units. Geometry optimization at the B3LYP‐631G level also confirms the noncoplanar arrangement of corroles with a dihedral angle of 64.8° between two corrole planes. The electron paramagnetic resonance (EPR) and magnetic characterization studies on the paramagnetic copper‐metalated dimer indicate that both copper ions behave as independent spins without any noticeable interaction. Results of fluorescence studies reveal a bathochromic shift of about 60 nm upon dimerization. The first hyperpolarizability (β) measured by using the hyper Rayleigh scattering (HRS) method reveals doubling of the β values on progressing from monomer to dimer, attributed to enhanced π conjugation. The use of copper dimers in the photocleavage of DNA is also explored. It is shown that the bimetallic copper dimer selectively cleaves the nucleic acids without affecting the proteins, suggesting a possible application of the copper complex in the removal of nucleic acid contaminants from protein extracts through a simple photolytic pathway.

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Section: Epr and Magnetic Propertiesmentioning

confidence: 99%

meso–meso‐Linked Corrole Dimers with Modified Cores: Synthesis, Characterization, and Properties

Sankar

Rath

Prabhuraja

et al. 2006

Chemistry A European J

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“…Other inorganic rings and cages that contain Al-N or Al-C units have been similarly investigated. [11] We have been interested in organostannoxanes for some time now and have recently shown the utility of these com- [ pounds to support hexa-ferrocene [12] and hexa-porphyrin [13] architectures. Encouraged by the success in the use of stannoxanes as inert cores for supporting a functional periphery we have turned our attention to the possibility of building multi-site coordination ligands based on stannoxane cores.…”

Section: Introductionmentioning

confidence: 99%

Transition Metal‐Assisted Hydrolysis of Pyrazole‐Appended Organooxotin Carboxylates Accompanied by Ligand Transfer

2007

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“…Only few reports are available where copper-(II) complexes promote DNA cleavage on their own (Reddy et al 2004, Verma et al 2004). For example, hexaporphyrin dyads were synthesized from n-butyl stannonic acid and 5-(4-carboxyphenyl)-10,15,20-tritolylporphyrin (H 2 TTP-CO 2 H) followed by copper insertion as artificial nucleases (Chandrasekhar et al 2005) The Cuhexaporphyrin 62 showed high nuclease activity towards DNA supercoils. Interestingly, DNA cleavage did not occur in the presence of the free base hexaporphyrin alone and a monomeric CuP complex also failed to cleave it.…”

Section: Photodynamic Therapy and Singlet Oxygen Productionmentioning

confidence: 99%

Photochemical Transformations Involving Porphyrins and Phthalocyanines

Sergeeva¹,

Senge²

2012

CRC Handbook of Organic Photochemistry and Photobiology, Third Edition - Two Volume Set

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A Lipophilic Hexaporphyrin Assembly Supported on a Stannoxane Core

Abstract: Lipophilic hexaporphyrin free-base and copper-metalated assemblies supported on a Sn6O6 core have been synthesized and characterized. The nuclease activity of the copper derivative has been studied.

Cited by 53 publications

References 29 publications

meso–meso‐Linked Corrole Dimers with Modified Cores: Synthesis, Characterization, and Properties

meso–meso‐Linked Corrole Dimers with Modified Cores: Synthesis, Characterization, and Properties

Transition Metal‐Assisted Hydrolysis of Pyrazole‐Appended Organooxotin Carboxylates Accompanied by Ligand Transfer

Photochemical Transformations Involving Porphyrins and Phthalocyanines

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