Tervalent-Metal Porphyrin-Phthalocyanine Heteroleptic Sandwich-Type Complexes. Synthesis, Structure, and Spectroscopic Characterization of Their Neutral, Singly-Oxidized, and Singly-Reduced States

Chabach, D.; Tahiri, Mohamed; Cian, A. De; Fischer, J.; Weiss, Raymond; Bibout, M. El Malouli

doi:10.1021/ja00138a009

Cited by 105 publications

(80 citation statements)

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“…The electronic absorption spectra of 1-9 were also measured ( Table 1). The data for the known compounds 1 [21] and 6 [19] were fully consistent with those reported previously. The UV-vis and near-IR spectra of the homoleptic (2 and 3) and heteroleptic (4 and 5) bis(phthalocyaninato) complexes closely resembled the spectra of analogous Eu(III) and Gd(III) complexes [7,24] and could be assigned in the same manner.…”

Section: Resultssupporting

confidence: 89%

“…During the preparation of a series of sandwich compounds Ln(Pc)(TPP) (Ln = La, Pr, Nd, Eu, Gd) from Ln(Pc)(acac) and H 2 (TPP), Weiss and coworkers isolated the protonated double-decker LaH(Pc)(TPP), which could be oxidized to La(Pc)(TPP) with phenoxathiinylium hexachloroantimonate [19]. This led to their proposition that the protonated species LnH(Pc)(TPP) are a common intermediate.…”

Section: Resultsmentioning

confidence: 99%

“…It is worth noting that the lower-energy near-IR band of these Y(III) complexes is significantly blue-shifted compared with that of the respective Eu and Gd complexes (1573-1693 nm). This can be attributed to the smaller ionic radius of Y(III) that results in a stronger p-p interaction [18,19,38].…”

Section: Resultsmentioning

confidence: 99%

“…Although a substantial number of such heteroleptic sandwich compounds have been synthesized recently, most of them are confined to lanthanide and group 4 transition metal complexes with unsubstituted phthalocyanine [14]. It has been reported that the electrochemical, spectroscopic and other physical properties of these double-decker complexes are related to the inter-ring distance in the molecule, which is determined by the ionic radius of the central metal ion and the strength of the metal-ligand bonds [3,[16][17][18][19]. Yttrium, which has a smaller ionic radius than the lanthanides (except Lu), also forms double-decker complexes, but examples are scarce.…”

Section: Introductionmentioning

confidence: 99%

“…Yttrium, which has a smaller ionic radius than the lanthanides (except Lu), also forms double-decker complexes, but examples are scarce. To our knowledge, only a few yttrium complexes, namely Y(P) 2 (P = Pc [17,20,21], Por [18,22,23]) and Y(Pc)(TPP) [19], have appeared in the literature, and heteroleptic complexes with a substituted phthalocyaninato ligand are extremely rare [14]. Very recently we have developed a useful procedure to prepare heteroleptic sandwiches Eu(P)(Pc) (P = Pc*(C 7 H 15 ) 8 , Pc*(OC 5 H 11 ) 8 , Por) which involves the cyclic tetramerization of phthalonitriles induced by the half-sandwich lanthanide complexes M(P)(acac) (P = Pc, Por) [24,25].…”

Section: Introductionmentioning

confidence: 99%

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Double-decker Yttrium(III) Complexes with Phthalocyaninato and Porphyrinato Ligands

Jiang

Xie

Choi

et al. 1999

J. Porphyrins Phthalocyanines

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A series of new yttrium(III) double-decker complexes with the same and different phthalocyaninato and porphyrinato ligands has been prepared. The homoleptic complexes Y ( P )2 ( P = Pc *(C7 H 15)8, Pc *( OC 5 H 11)8; Pc * = 2,3,9,10,16,17,23,24-octasubstituted phthalocyaninate) have been synthesized by treating yttrium(III) acetylacetonate ( Y ( acac )3· H 2 O ) with the phthalonitriles C 6 H 2 R 2( CN )2 ( R = C 7 H 15, OC 5 H 11) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The heteroleptic analogues Y ( P )( Pc ) ( P = Pc *( C 7 H 15)8, Pc *( OC 5 H 11)8; Pc = unsubstituted phthalocyaninate) and Y ( P )( Por ) ( P = Pc , Pc *( C 7 H 15)8; Por = meso-tetraphenylporphyrinate (TPP), meso-tetra(4-pyridyl)porphyrinate (TPyP)) have been prepared by the base-catalysed tetramerization of the corresponding phthalonitriles using Y ( P )( acac ) ( P = Pc , TPP , TPyP ) as templates. The syntheses along with the spectroscopic and electrochemical properties of these novel double-deckers are described.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Double-decker Yttrium(III) Complexes with Phthalocyaninato and Porphyrinato Ligands

Jiang

Xie

Choi

et al. 1999

J. Porphyrins Phthalocyanines

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Heteroleptic Rare Earth Double-Decker Complexes with Porphyrinato and 2,3-Naphthalocyaninato Ligands − Preparation, Spectroscopic Characterization, and Electrochemical Studies

Jiang

Liu

Cheng

et al. 2001

Eur. J. Inorg. Chem.

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A series of RE(Nc)(TBPP) (1−12) complexes [RE = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Y, Ho, Er, Tm; Nc = 2,3‐naphthalocyaninate; TBPP = meso‐tetrakis(4‐tert‐butylphenyl)porphyrinate] and Eu[Nc(tBu)4](TClPP) [Nc(tBu)4 = tetra(tert‐butyl)‐2,3‐naphthalocyaninate; TClPP = meso‐tetrakis(4‐chlorophenyl)porphyrinate] (13) have been prepared by a one‐pot procedure which involves the treatment of RE(acac)3·nH2O (acac = acetylacetonate) with the corresponding metal‐free porphyrins and naphthalonitriles in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in n‐octanol. These novel double‐deckers have been spectroscopically characterized. A one‐electron reduction and three one‐electron oxidations have been revealed by electrochemical methods. The potentials of all these processes depend linearly on the ionic radii of the central metal ions, giving a relatively large potential difference (0.50−0.57 V) between the first oxidation and the first reduction processes.

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Synthesis, Structure, Spectroscopic Properties, and Electrochemistry of Rare Earth Sandwich Compounds with Mixed 2,3-Naphthalocyaninato and Octaethylporphyrinato Ligands

et al. 2001

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A series of 14 heteroleptic rare earth sandwich complexes [M(III)-(nc)(oep)] (M=Y, La-Lu except Ce and Pm; nc=2,3-naphthalocyaninate; oep = octaethylporphyrinate) have been prepared by a one-pot procedure from corresponding [M(acac)3] . nH2O (acac = acetylacetonate), metal-free porphyrin H2(oep), and naphthalonitrile the presence of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) in n-octanol. The molecular structures of four of these complexes (M = Sm, Gd, Y, Lu) are isostructural, exhibiting a slightly distorted square antiprismatic geometry with two domed ligands. The interplanar distance decreases from 2.823 to 2.646 A along the series as a result of lanthanide contraction. The whole series of complexes have also been characterized spectroscopically. All the electronic absorptions, except the two B-bands due to nc and the oep rings, are metal-dependent, indicating that there are substantial pi-pi interactions. The hole or the unpaired electron in these double-deckers is delocalized over both macrocyclic ligands, as evidenced by the co-appearance of the IR marker bands for the nc*- (1315-1325 cm(-1)) and oep*- (1510-1531 cm(-1)) T radical ions. Three one-electron oxidation couples and up to three one-electron reduction couples have been revealed by electrochemical methods. All the potentials are linearly dependent on the size of the metal center. The changes in absorption spectra during the first electro-oxidation and reduction of the La(III), Eu(III), and Y(III) double-deckers have also been studied spectroelectrochemically. The spectral data recorded for [M(III)(nc)(oep)]-(M = Y, La-Lu except Ce and Pm) reduced chemically with hydrazine hydrate are in accord with those obtained by spectroelectrochemical methods. The first heteroleptic naphthalocyaninate-containing triple-deckers [M(III)2(nc)-(oep)2] (M = Nd, Eu) have also been prepared by a raise-by-one-story method by using [M(III)(nc)(oep)] (M = Nd, Eu), [M(acac)3] . nH2O (M = Nd, Eu), and H2(oep) as starting materials. The compounds adopt a symmetrical triple-decker structure with two outer oep rings and one inner nc ring, which has been confirmed by 'H NMR spectroscopy and X-ray structural determination of the Nd complex. Both compounds give a near-IR absorption at 1021 nm (for M=Nd) or 1101 nm (for M = Eu), which has rarely been observed for neutral (or hole-free) triple-decker complexes and can be ascribed to the lowest-energy Q'(0, 0) transition. Similarly to the double-decker analogues. these triple-decker complexes undergo a series of one-electron transfer processes with a relatively small potential gap (1.1 -1.2 V) between the first oxidation and the first reduction.

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Tervalent-Metal Porphyrin-Phthalocyanine Heteroleptic Sandwich-Type Complexes. Synthesis, Structure, and Spectroscopic Characterization of Their Neutral, Singly-Oxidized, and Singly-Reduced States

Cited by 105 publications

References 0 publications

Double-decker Yttrium(III) Complexes with Phthalocyaninato and Porphyrinato Ligands

Double-decker Yttrium(III) Complexes with Phthalocyaninato and Porphyrinato Ligands

Heteroleptic Rare Earth Double-Decker Complexes with Porphyrinato and 2,3-Naphthalocyaninato Ligands − Preparation, Spectroscopic Characterization, and Electrochemical Studies

Synthesis, Structure, Spectroscopic Properties, and Electrochemistry of Rare Earth Sandwich Compounds with Mixed 2,3-Naphthalocyaninato and Octaethylporphyrinato Ligands

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