Synthesis and electronic properties of diacetylene- and vinylene-groups connected octaethylporphyrin tetramer

Higuchi, Hiroyoshi; Maeda, Takao; Miyabayashi, Keiko; Miyake, Mikio; Yamamoto, Kōji

doi:10.1016/s0040-4039(02)00494-x

Cited by 14 publications

(3 citation statements)

References 13 publications

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“…[21][22][23][24][25][26] Alkynyl porphyrin units have been the focus of intensive investigations by Arnold, [27][28][29][30][31] Anderson, [12,13,[32][33][34][35][36][37][38][39][40][41][42][43][44][45] Therien, [6,7,11,[46][47][48][49][50][51][52][53][54] Osuka, [35,36,55,56] and others. [57][58][59][60][61][62][63][64][65]…”

Section: Introductionmentioning

confidence: 99%

Charge‐Transfer State and Large First Hyperpolarizability Constant in a Highly Electronically Coupled Zinc and Gold Porphyrin Dyad

Fortage¹,

Scarpaci²,

Viau³

et al. 2009

Chemistry A European J

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We report the synthesis and the characterizations of a novel dyad composed of a zinc porphyrin (ZnP) linked to a gold porphyrin (AuP) through an ethynyl spacer. The UV/Vis absorption spectrum and the electrochemical properties clearly reveal that this dyad exhibits a strong electronic coupling in the ground state as evidenced by shifted redox potentials and the appearance of an intense charge-transfer band localized at lambda = 739 nm in dichloromethane. A spectroelectrochemical study of the dyad along with the parent homometallic system (i.e., ZnP-ZnP and AuP-AuP) was undertaken to determine the spectra of the reduced and oxidized porphyrin units. Femtosecond transient absorption spectroscopic analysis showed that the photoexcitation of the heterometallic dyad leads to an ultrafast formation of a charge-separated state ((+)ZnP-AuP(*)) that displays a particularly long lifetime (tau = 4 ns in toluene) for such a short separation distance. The molecular orbitals of the dyad were determined by DFT quantum-chemical calculations. This theoretical study confirms that the observed intense band at lambda = 739 nm corresponds to an interporphyrin charge-transfer transition from the HOMO orbital localized on the zinc porphyrin to LUMO orbitals localized on the gold porphyrin. Finally, a Hyper-Rayleigh scattering study shows that the dyad possesses a large first molecular hyperpolarizability coefficient (beta = 2100x10(-30) esu at lambda = 1064 nm), thus highlighting the valuable nonlinear optical properties of this new type of push-pull porphyrin system.

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Section: Introductionmentioning

confidence: 99%

Charge‐Transfer State and Large First Hyperpolarizability Constant in a Highly Electronically Coupled Zinc and Gold Porphyrin Dyad

Fortage¹,

Scarpaci²,

Viau³

et al. 2009

Chemistry A European J

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“…16 Typical splitting values for the first oxidation potentials in porphyrin conjugated dimers are, respectively, 80 mV, 240 mV, or 400 mV for the ethylenyl and ethynyl linked dimers or for Osuka's triply fused diporphyrins. [15][16][17] At this stage, intramolecular coulombic effects (between two radical cations and then between two dications) seem to be the most reasonable explanation for the clear splitting observed here (the shortest distance between the two porphyrins, C-meso to C-meso is 6.85 A ˚). However, in porphyrin dimers with similar but even shorter palladium(II) linkages, no splitting was observed.…”

Section: Communicationmentioning

confidence: 99%

“…15 The values reported here can be compared with the 80 mV splitting reported by 5 Higuchi for an ethylenyl linked NiOEP dimer. 16 Typical splitting values for the first oxidation potentials in porphyrin conjugated dimers are respectively 80 mV, 240 mV, or 400 mV for the ethylenyl and ethynyl linked dimers or for Osuka's triply fused diporphyrins. 15 At this stage, intramolecular coulombic effects (between two radical cations and then between two dications) seems the most reasonable explanation for the clear splitting observed 30 here (the shortest distance between the two porphyrins, Cmeso to C-meso is 6.85 Å).…”

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confidence: 99%

Carbene spacers in bis-porphyrinic scaffolds

et al. 2012

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Homo‐ and Heteronuclear meso,meso‐(E)‐Ethene‐1,2‐diyl‐Linked Diporphyrins: Preparation, X‐ray Crystal Structure, Electronic Absorption and Emission Spectra and Density Functional Theory Calculations

Locos

Bašić

McMurtrie

et al. 2012

Chemistry A European J

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Homo- and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M(2)10 (M(2) =H(2)/Ni, Ni(2), Ni/Zn, H(4), H(2)Zn, Zn(2)) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H(2), Ni, and ZnTriPP on the other (M(2)11), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, (1)H NMR spectra, and for the Ni(2) bis(TriPP) complex Ni(2)10, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni(II) porphyrins, and the (E)-C(2)H(2) bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H(4)10 and H(2)Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni(2)10 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV.

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Synthesis and electronic properties of diacetylene- and vinylene-groups connected octaethylporphyrin tetramer

Cited by 14 publications

References 13 publications

Charge‐Transfer State and Large First Hyperpolarizability Constant in a Highly Electronically Coupled Zinc and Gold Porphyrin Dyad

Charge‐Transfer State and Large First Hyperpolarizability Constant in a Highly Electronically Coupled Zinc and Gold Porphyrin Dyad

Carbene spacers in bis-porphyrinic scaffolds

Homo‐ and Heteronuclear meso,meso‐(E)‐Ethene‐1,2‐diyl‐Linked Diporphyrins: Preparation, X‐ray Crystal Structure, Electronic Absorption and Emission Spectra and Density Functional Theory Calculations

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