Redox Gradations in Ruthenium Porphycene Complexes and the Porphyrin Analogs: Axial and Macrocyclic Ligand Effects

Okawara, Toru; Abe, Masaaki; Shimakoshi, Hisashi; Hisaeda, Yoshio

doi:10.1246/cl.2008.906

Cited by 15 publications

(6 citation statements)

References 17 publications

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“…Complex 1 was synthesized by photolysis of [Ru II (TPrPc) (CO) (MeOH)] in toluene containing a large excess of btp to allow dissociation of CO and subsequent coordination of the pyridyl moiety in btp to the axial sites . The remarkable utility of the ligand btp for oxidative electropolymerization of transition-metal complexes has been previously described .…”

mentioning

confidence: 73%

An Electropolymerized Crystalline Film Incorporating Axially-Bound Metalloporphycenes: Remarkable Reversibility, Reproducibility, and Coloration Efficiency of Ruthenium(II/III)-Based Electrochromism

et al. 2015

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Oxidative electropolymeization of an axially bound, bithiophene-pyridine complex of ruthenium(III)-porphycene [Ru(TPrPc) (btp)2]PF6 (1) gives a submicrometer-thick, polymeric film on an ITO electrode with a crystalline morphology. The polymeric film, the first example of axially linked multimetalloporphycene coordination arrays, exhibits highly stable and reproducible electrochromic response with high electrochromic efficiency upon electrochemical control over the metal-centered electron transfer process (Ru(II)/Ru(III)).

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mentioning

confidence: 73%

An Electropolymerized Crystalline Film Incorporating Axially-Bound Metalloporphycenes: Remarkable Reversibility, Reproducibility, and Coloration Efficiency of Ruthenium(II/III)-Based Electrochromism

et al. 2015

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“…Insertion of ruthenium into the porphycene skeleton was achieved for 13 , , 19 , 200 – 202 (Scheme ), 224 (Scheme ), and 233 (Scheme , below). Upon irradiation of benzene solutions containing pyridine, ruthenium(II) carbonyl complexes of 13 and 19 undergo photosubstitution and yield bis-pyridine complexes. , The process is faster in porphycenes than in the corresponding 2,3,7,8,12,13,17,18-octaethylporphyrin analogue.…”

Section: Electronic Spectroscopymentioning

confidence: 99%

“…128,129,134,137 Moreover, the absorption is sensitive to the spin state of the metal. 138 Insertion of ruthenium into the porphycene skeleton was achieved for 13, 139,140 19, 140 139,140 The process is faster in porphycenes than in the corresponding 2,3,7,8,12,13,17,18-octaethylporphyrin analogue.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Spectroscopy and Tautomerization Studies of Porphycenes

2016

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Tautomerization in porphycenes, constitutional isomers of porphyrins, is strongly entangled with spectral and photophysical parameters. The intramolecular double hydrogen transfer occurring in the ground and electronically excited states leads to uncommon spectroscopic characteristics, such as depolarized emission, viscosity-dependent radiationless depopulation, and vibrational-mode-specific tunneling splittings. This review starts with documentation of the electronic spectra of porphycenes: Absorption and magnetic circular dichroism are discussed, together with their analysis based on the perimeter model. Next, photophysical characteristics are presented, setting the stage for the final part, which discusses the developments in research on tautomerism. Porphycenes have been studied in different experimental regimes: molecules in condensed phases, isolated in supersonic jets and helium nanodroplets, and, recently also on the level of single molecules investigated by optical and scanning probe microscopies. Because of the rich and detailed information obtained from these diverse investigations, porphycenes emerge as very good models for studying the complex, multidimensional phenomena involved in the process of intramolecular double hydrogen transfer.

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“…1 . The absorption pattern of 1 is thus very similar to the sum of absorption bands of a pyridine-coordinated ruthenium(II) porphycene [Ru(TPrPc)(CO)(pyridine)] (2') [15,16] and 3 ( Fig. 1), indicating that the electronic features for the individual chromophores in 1 remain almost unchanged upon coordinative linkage.…”

Section: Communicationsmentioning

confidence: 62%

Synthesis, Characterizations, and Intramolecular Quenching Behavior of an Axially-Linked Trinuclear Molecular Wire Containing Ruthenium(II) Porphycenes

Abe¹,

Ashigara²,

Okawara³

et al. 2015

Rapid Communication in Photoscience

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ABSTRACT:A new trinuclear complex [Ru(TPrPc)(CO)] 2 [Ru(pytpy) 2 ](PF 6 ) 2 (TPrPc = 2,7,12,17-tetra-npropylporphycenato dianion and pytpy = 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine) has been synthesized and characterized as the first example of a discrete molecular wire containing metalloporohycenes as a building block. The trinuclear complex shows multiple-step redox behavior in 0.1 M n-Bu 4 NPF 6 -dichloromethane. The mononuclear [Ru(pytpy) 2 ] 2+ precursor shows emission at 640 nm (deaerated acetone, 298 K) upon illumination at the metal-to-ligand charge transfer (MLCT) band at 495 nm, but the trinuclear molecular wire is found to be non-emissive upon photoexcitation at the central [Ru(pytpy) 2 ] 2+ entity, indicating an efficient quenching ability of the axially-linked, ruthenium(II)-porphycene chromophores in an intramolecular fashion.Porphycene is one of the constitutional isomers of porphyrin with a tetrapyrrolic N 4 cavity in a rectangular shape [1][2][3][4]. Chemistry of porphycene and metalloporphycene complexes [5,6] has been of considerable interest due to their intense absorption in the visible region [7], utility as photodynamic therapy (PDT) agents [8], and substrate binding and activation [9]. Recently, porphycenes have been used as functional building blocks incorporated into carbon nanomaterials [10].Stable axial coordination in metalloporphyrin complexes has been convenient and powerful molecular approach to construct a novel series of redox-and photo-functional molecular assemblies, such as molecular wires via coordinative linkage [11]. Actually, the construction of well-defined, metalloporphyrin-based ensembles via axial coordination has constituted active research areas in the metallosupramolecular chemistry [12,13]. As a multicomponent molecular wire, Branda and the coworker have previously described [17,18] in acetone for 24 h at room temperature and, after workup, isolated as a bluish green solid in a 58% yield [19]. The compound was fully characterized by various spectroscopic methods, mass spectrometry, and cyclic voltammetry.1 H NMR spectroscopy (acetone-d 6 ) reveals the formation of the expected trinuclear structure comprised of [Ru(TPrPc)(CO)] and [Ru(pytpy) 2 ] 2+ moieties in a 2:1 ratio. A noticeable ring current effect of the TPrPc 2-ligand is seen for a resonance due to 2,6-H of the pyridyl group in pytpy which appears at  1.18. ESI-MS shows a parent mass envelope at m/z = 967.6 with a peak interval of 0.5, indicating formation of the anticipated trinuclear complex with an overall charge of +2. In addition, an IR spectrum (KBr pellet) exhibits a strong (CO) peak ascribed to the [Ru(TPrPc)(CO)] group at 1930 cm -1 which is comparable with that of the monomeric precursor 2 (1932 cm -1 ).

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Redox Gradations in Ruthenium Porphycene Complexes and the Porphyrin Analogs: Axial and Macrocyclic Ligand Effects

Cited by 15 publications

References 17 publications

An Electropolymerized Crystalline Film Incorporating Axially-Bound Metalloporphycenes: Remarkable Reversibility, Reproducibility, and Coloration Efficiency of Ruthenium(II/III)-Based Electrochromism

An Electropolymerized Crystalline Film Incorporating Axially-Bound Metalloporphycenes: Remarkable Reversibility, Reproducibility, and Coloration Efficiency of Ruthenium(II/III)-Based Electrochromism

Spectroscopy and Tautomerization Studies of Porphycenes

Synthesis, Characterizations, and Intramolecular Quenching Behavior of an Axially-Linked Trinuclear Molecular Wire Containing Ruthenium(II) Porphycenes

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