ChemInform Abstract: First Example of a Trimeric Metalloporphyrin. Synthesis, Electrochemical, and Spectroelectrochemical Studies of ((P)Th(OH)2)3 Where P is the Dianion of Octaethyl‐ or Tetraphenylporphyrin. Crystal Structure of a Dihydrated Trinuclear Complex of Dihydroxy(5,10,15,20‐tetraphenylporphinato)thorium(IV) Heptane Solvate.

Kadish, Karl M.; Liu, Y. H.; Anderson, James E.; Charpin, P.; Chevrier, G.; Lance, M.; Nierlich, Martine; Vigner, D.; Dormond, A.; Belkalem, B.; Guilard, Roger

doi:10.1002/chin.198852217

Cited by 3 publications

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“…The three Pc rings have bowl‐shaped conformations, with dihedral angles between isoindolene quadrants of 12.64–28.73° and Dy III centres that sit 1.268, 1.273, and 1.360 Å out of their respective Pc planes. Although no such trinuclear PcM‐based clusters are known, a related porphyrin‐containing structure, [(TPP)Th(OH) 2 ] 3 , has been reported, as well as simpler dinuclear PcM‐based μ‐oxo derivatives of the form [(L)PcTM‐ O ‐TMPc(L)] (TM=Ti, Cr, Mn, and Fe) and Pc‐free clusters of lanthanide hydroxides . The CV of Li(PcDy) 3 (OH) 4 (H 2 O) in THF shows two irreversible reduction peaks at −0.6 and −0.95 V, assigned to ring reduction to Pc 3− and Pc 4− , respectively, lower than compared to PcDyCl (−0.2 V and −0.6 V), and a reversible ring‐oxidation peak at 0.6 V.…”

Section: Methodsmentioning

confidence: 99%

Structural Diversity of F‐Element Monophthalocyanine Complexes

Zhou

McKearney

Leznoff

2020

Chemistry A European J

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The preparation and structural characterization of as eries of lanthanide and uranium(IV)p hthalocyanine halide complexes were achieved by reaction of the corresponding metal halide with Li 2 Pc. Ap reliminarys urvey of their reactivity includes ring reduction of Li(THF) 4 [PcUCl 3 ] with KC 8 leading to the first structurally characterized Pc 4À actinide complex, hydrolysis of PcDyCl(DMSO) to PcDyOH(H 2 O) 3 and preparation of au nique trimeric triangular Li(PcDy) 3 (OH) 4 (H 2 O) cluster.Macrocyclic phthalocyanines, porphyrins, andt heir metal complexes are widelyu sed for applications, such as dyes, pigments, [1] catalysts, [2] and photosensitizes for photodynamic cancert herapy with singlet oxygen. [3] The vast majority of metallophthalocyanine (PcM) complexes utilize transition metals,w ith ap articularf ocus on the late first row elements due to their good fit with the Pc-holeand their very high stability. Pc-complexes of fe lements (Ln = lanthanide;A c = actinide), which were first reported in 1965, [4] are much less investigated, with the notable exceptiono fb is-phthalocyanine sandwich complexes of the form [Pc 2 Ln] À and their more elaborate multidecker analogues, such as Pc 3 Ln 2 , [4,5] whicha re favoured due to the large ionic radii andh igh coordination numbers of the f-block elements, anda re of particulari nterest for single-molecule-magnet applications (especially for Ln = Dy,T b, Er). [6,7] However, furtherc hemistry at the metal site is limited in these Pc 2 -based systemsd ue to the steric and electronic saturation of the Ln centre. The less developed mono-PcLnXo rP cAcX 2 systems have mostly focused on oxy-anions as the axial X-group, with afew examples of X = halide; [8,9] however,t here are very few structurally characterizeds ystems, and their reactivity chemistry is ripe for furtherd evelopment. Herein, we report the synthesis, structure, and preliminaryr eactivity survey of PcM halide materials for both 4f and 5f metals, illustrating a Scheme1.Synthesis of PcDyCl(DMSO), PcErCl(THF), and Li(THF) 4 [PcUCl 3 ]. "Solvent" in PcLn-product = DMSO or THF,depending on the recrystallization conditions(seetext).[a] Dr.

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Section: Methodsmentioning

confidence: 99%

Structural Diversity of F‐Element Monophthalocyanine Complexes

Zhou

McKearney

Leznoff

2020

Chemistry A European J

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“…53 As far as we know, only one example of trinuclear thorium arrangement has been reported in the literature. 54 The structure of this thorium cluster differs largely from our compound because the three thorium cations are bridged by six μ 2 -hydroxo atoms to form a trinuclear [Th 3 (OH) 6 ] 6+ unit; however, no μ 3 -oxo bridge is present. In this literature compound, each thorium atom is thus coordinated to four μ 2 -hydroxo groups.…”

Section: Resultsmentioning

confidence: 93%

Stabilization of Tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) Clusters by the [α-SiW₉O₃₄]^10– Polyoxometalate

et al. 2015

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The reaction of Na10[α-SiW9O34] with tetravalent metallic cations such as 4f ((NH4)2Ce(NO3)6), 5d (HfCl4), or 5f (UCl4 and Th(NO3)4) in a pH 4.7 sodium acetate buffer solution leads to the formation of four sandwich-type polyoxometalates [Ce4(μ(3)-O)2(SiW9O34)2(CH3COO)2](10-) (1), [U4(μ(3)-O)2(SiW9O34)2(CH3COO)2](10-) (2), [Th3(μ(3)-O)(μ(2)-OH)3(SiW9O34)2](13-) (3), and [Hf3(μ(2)-OH)3(SiW9O34)2](11-) (4). All four compounds consist of a polynuclear cluster fragment stabilized by two [α-SiW9O34](10-) polyanions. Compounds 1 and 2 are isostructural with a tetranuclear core (Ce4, U4), while compound 3 presents a trinuclear Th3 core bearing a μ(3)-O-centered bridge. It is an unprecedented configuration in the case of the thorium(IV) cluster. Compound 4 also possesses a trinuclear Hf3 core but with the absence of the μ(3)-O bridge. The molecules have been characterized by single-crystal X-ray diffraction, (183)W and (29)Si nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) analysis.

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“…The covalently linked molecular assemblies can provide a close mimic of complicated chromophore compositions of the light-harvesting complex [1][2][3]. In addition, cofacial trimer porphyrins have attracted considerable interest in the area of catalysis of electrochemical reduction of oxygen to water by a four-electron mechanism [6,7]. Covalently linked trimer porphyrins are known to display charge separation and electron transfer reactions [4,5].…”

Section: Introductionmentioning

confidence: 99%

Covalently Linked Tetraphenylporphyrin Trimers and Tetramers and their Coordination Behaviour

Vaijayanthimala

Krishnan

1997

J. Porphyrins Phthalocyanines

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Several covalently linked tetraphenyl porphyrin trimers and tetramers bearing ethylene oxide bridges originating from the m and p positions of adjacent and/or opposite meso-aryl groups have been synthesized and characterized by fast atom bombardment mass spectroscopy, 1 H NMR, optical absorption and emission spectroscopies. The fully and partially metallated zinc(II) and copper(II) derivatives have been prepared and their photophysical properties are outlined. The steady-state and time-resolved fluorescence studies of the heterotrimers indicate efficient energy transfer from the ZnP to the H 2 P unit. The efficiency and rate of energy transfer are dependent on the number of free-base units in the hetero-oligomers and the geometrical position of the porphyrin units. The heterotrimers consisting of one, two and three zinc(II) centres bind 4,4″-bipyridyl in different modes as revealed by the nature of binding curves. The bipyridyl ligand functions as a chelate in the complexes of biszinc(II) porphyrin trimers while two bipyridyls bind to trizinc(II) porphyrin trimers with one ligand functioning as a chelate and another exhibiting monodentate coordination behaviour. The folding of two ZnP units is clearly seen in the complexes of bis and triszinc(II) trimers with bipyridyl, which is substantiated by molecular mechanics calculations. Axial ligation studies with trimers show that the preorganization of porphyrin hosts is necessary for recognition of the guest. The binding of bipyridyl to the trimers is followed by global conformational changes and this behaviour is analogous to activated complex binding in induced-fit enzymes.

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Abstract: The reaction of dichlorothorium complexes of octaethyl‐ or tetraphenylporphyrin with sodium carbonate in oxygen‐free THF gives the corresponding dihydroxo‐porphyrinatothorium compounds as trimers (80 and 82% yield).

Cited by 3 publications

References 1 publication

Structural Diversity of F‐Element Monophthalocyanine Complexes

Structural Diversity of F‐Element Monophthalocyanine Complexes

Stabilization of Tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) Clusters by the [α-SiW₉O₃₄]^10– Polyoxometalate

Covalently Linked Tetraphenylporphyrin Trimers and Tetramers and their Coordination Behaviour

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Abstract: The reaction of dichlorothorium complexes of octaethyl‐ or tetraphenylporphyrin with sodium carbonate in oxygen‐free THF gives the corresponding dihydroxo‐porphyrinatothorium compounds as trimers (80 and 82% yield).

Cited by 3 publications

References 1 publication

Structural Diversity of F‐Element Monophthalocyanine Complexes

Structural Diversity of F‐Element Monophthalocyanine Complexes

Stabilization of Tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) Clusters by the [α-SiW9O34]10– Polyoxometalate

Covalently Linked Tetraphenylporphyrin Trimers and Tetramers and their Coordination Behaviour

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Stabilization of Tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) Clusters by the [α-SiW₉O₃₄]^10– Polyoxometalate