Metal-Mediated Multi-Porphyrin Discrete Assembliesand Their Photoinduced Properties

Iengo, Elisabetta; Scandola, Franco; Alessio, Enzo

doi:10.1007/430_025

Cited by 41 publications

(25 citation statements)

References 87 publications

(86 reference statements)

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“…20% lower than that of the parent porphyrin (ESI), † as expected because of the peripheral heavy atoms. 20 Finally, the tetra-ruthenated porphyrin conjugate [bpy 4 -PP{Ru( [12]aneS4} 4 ][CF 3 SO 3 ] 8 (11, Fig. 12), in which the peripheral Ru fragments have no labile ligands, was prepared in good yield by reaction of bpy 4 -PP with a slight excess of the Ru(II) precursors [Ru( [12]aneS4)(dmso-S)(H 2 O)][CF 3 SO 3 ] 2 ([12]aneS4 = 1,4,7,10-tetrathiacyclododecane).…”

Section: Conjugates Through Two-bond Coordinationmentioning

confidence: 99%

Synthetic strategies towards ruthenium–porphyrin conjugates for anticancer activity

et al. 2009

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The conjugation of porphyrins to metal fragments is a strategy for making new compounds that are expected to combine the phototoxicity and the tumour-localization properties of the porphyrin chromophore with the cytotoxicity of the metal fragment for additive antitumour effect. We report here the preparation of new classes of porphyrin-ruthenium conjugates with potential bio-medical applications. Ruthenium was chosen because several Ru compounds have shown promising anticancer activity. The conjugation with the porphyrin moiety was accomplished either through peripheral pyridyl rings (e.g.meso-4'-tetrapyridylporphyrin, 4'TPyP) or through bpy units (e.g.meso-(p-bpy-phenyl)porphyrins, bpy(n)-PPs, n = 1-4). The number of Ru fragments attached to the porphyrins ranges from 1 to 4 and the total charge of the conjugates from -4 to +8. Different types of peripheral fragments, both Ru(III) and Ru(II), have been used: in some cases they are structurally similar to established anticancer compounds. Examples are [Na](4)[4'TPyP{trans-RuCl(4)(dmso-S)}(4)] (2), that bears four NAMI-type Ru(III) fragments, or [4'TPyP{Ru([9]aneS3)(en)}(4)][CF(3)SO(3)](8) (3) and [bpy(4)-PP{Ru([9]aneS3)(dmso-S)}(4)][CF(3)SO(3)](8) (9) (en = ethane-1,2-diamine, [9]aneS3 = 1,4,7-trithiacyclononane) that have four half-sandwich Ru(II) compounds. The Ru fragments may either contain one or more labile ligands, such as in 2 or in 9, or be coordinatively saturated and substitutionally inert, such as in 3 or in [bpy(4)-PP{Ru([12]aneS4)}(4)][CF(3)SO(3)](8) (11) ([12]aneS4 = 1,4,7,10-tetrathiacyclododecane). Most of the ruthenium-porphyrin conjugates described in this work are soluble--at least moderately--in aqueous solution and are thus suitable for biological investigations, in particular for cytotoxicity and photo-cytotoxicity tests.

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Section: Conjugates Through Two-bond Coordinationmentioning

confidence: 99%

Synthetic strategies towards ruthenium–porphyrin conjugates for anticancer activity

et al. 2009

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“…Many discrete metallosupramolecular assemblies and coordination polymers based on porphyrin building blocks are known [1][2][3].…”

Section: Introductionmentioning

confidence: 99%

1D and 2D solid-state metallosupramolecular arrays of freebase 5,10,15,20-tetra(4-pyridyl)porphyrin, peripherally linked by zinc and manganese ions

Seidel

Oppel

2009

Struct Chem

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Freebase 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP) is able to assemble into crystalline rigid 1D and 2D metallosupramolecular arrrays via exocyclic coordination with tetracoordinate and hexacoordinate metal ions, respectively. In this contribution we report on two coordination polymers of l 4 -bridging freebase TPyP with zinc and manganese halide moieties. The structure of [(ZnBr 2 ) 2 TPyP] Á 6 TCE (2) (TCE = 1,1,2,2-tetrachloroethane) consists of 1D polymeric chains. The topology of [(MnCl 2 )TPyP] Á 6 TCE (3) is the (4,4) square grid type. The crystal structure of the known compound [(HgI 2 ) 2 TPyP] Á 4 TCE (1) was redetermined by X-ray crystallography.

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“…3) Metalloporphyrins bearing two trans axial ligands, such as tin(IV) and silicon(IV) porphyrins, which have symmetrical molecular structures. While supramolecular assembly of metalloporphyrins based on their coordination chemistry has been intensively and extensively studied during the past decades,4a,c, 9a–d, 10a–c the effects of their molecular geometry due to the number of the axial ligands on the assembly properties have been relatively less addressed. The latter aspect is of practical importance, since it could provide a wealth of information for porphyrin engineering, and give deep insight into supramolecular assembly of metalloporphyrins.…”

Section: Introductionmentioning

confidence: 99%

Interfacial Molecular Assemblies of Metalloporphyrins with Two Trans or One Axial Ligands

Yao¹,

Qiu²,

Chen³

et al. 2010

ChemPhysChem

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Molecular assemblies of metalloporphyrins trans-dichloro(5,10,15,20-tetra-p-tolylporphyrinato)tin(IV) (SnCl2TPPMe) and trans-dihydroxo(5,10,15,20-tetra-p-tolylporphyrinato)tin(IV) (Sn(OH)2TPPMe), which have two trans axial ligands, as well 5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphine iron(III) chloride (FeClTPPOMe) and 5,10,15,20-tetraphenyl-21H,23H-porphine manganese(III) chloride (MnClTPP), which have one axial ligand, are interfacially organized by Langmuir and Langmuir-Blodgett (LB) techniques. SnCl2TPPMe and Sn(OH)2TPPMe form nanofibrous structures which can display distinct supramolecular chirality, although the molecular units themselves are achiral, while FeClTPPOMe and MnClTPP form irregular nanoparticles that display negligible supramolecular chirality. An interpretation in terms of the effects of the axial ligands is proposed for this interesting phenomenon. Moreover, compared with assemblies of the diprotonated free-base porphyrins, which are fabricated by interfacial (air/2.4 M HCl) organization of free-base porphyrin, those of SnCl2TPPMe and Sn(OH)2TPPMe display higher stability in terms of supramolecular chirality. These results indicate that the assembly properties of metalloporphyrins can essentially be affected by the axial ligands that are attached to their chromophores, and that stable chiral porphyrin supramolecular associations can be easily produced by using achiral metalloporphyrins bearing two trans axial ligands.

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Metal-Mediated Multi-Porphyrin Discrete Assembliesand Their Photoinduced Properties

Cited by 41 publications

References 87 publications

Synthetic strategies towards ruthenium–porphyrin conjugates for anticancer activity

Synthetic strategies towards ruthenium–porphyrin conjugates for anticancer activity

1D and 2D solid-state metallosupramolecular arrays of freebase 5,10,15,20-tetra(4-pyridyl)porphyrin, peripherally linked by zinc and manganese ions

Interfacial Molecular Assemblies of Metalloporphyrins with Two Trans or One Axial Ligands

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