Electrochemistry and spectroelectrochemistry of zirconium(IV) and hafnium(IV) phthalocyanines with b-diketone axial ligands

Ou, Zhongwen; Zhan, Riqiang; Tomachynski, L.; Chernii, Viktor; Kadish, Karl M.

doi:10.6060/mhc2011.3.04

Cited by 18 publications

(18 citation statements)

References 29 publications

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“…35 Vv ersus Fc/Fc + resulted in the emergenceo fr edshifted bands at 771 and 861 nm ( Figure 6) at the expense of the Qb and at 697 nm and the Soret band at 416 nm. Such spectralc hanges are associated with the formation of the p-anion radical, that is, MPc À C. [26,[29][30][31][32] The CV experiment for GaClPcF64 5 revealed three quasi-reversible reductions, in good agreement with the low-temperature DPV measurement ( Figure 7). The first reduction potential was detected at À0.25 V, the second reduction waso bserved at À0.65 V, and the third reduction of GaClPcF 64 5 was found at ar edox potential of À1.13 Vv ersus Fc/Fc + .C ontrolled potential electrolysis of aT HF solution of GaClPcF 64 5 at À0.36 V versus Fc/Fc + resulted in the emergence of redshifted bands at 823 and9 27 nm at the expense of the Q-band at 691 nm and the Soret band at 388 nm (Figure 7).…”

Section: Electrochemistrysupporting

confidence: 56%

“…The appearance of sharpa bsorption bands between the Qa nd Soret bands is an indication of dianion formation, namely MPc 2À ,u pon two-electron ring reduction. [29,30] It became clear that the first reduction potential, due to the very low cathodic current, is masked by thes trong background current. Finally, the room-temperature DPV measurement revealed that 6 undergoes af irst reduction at apotential ofÀ0.28 Vv ersus Fc/Fc + .T he second reduction for 6 occurs at ap otential of À0.54 V and the third reduction at À1.03 Vv ersus Fc/Fc + .…”

Section: Electrochemistrymentioning

confidence: 99%

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Highly Thermostable, Non‐oxidizable Indium, Gallium, and Aluminium Perfluorophthalocyanines with n‐Type Character

Łapok

Obłoza

Nowakowska

2016

Chemistry A European J

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Perfluorophthalocyanines incorporating three-valent metals, namely In(Cl), Ga(Cl), and Al(Cl), have been synthesized and characterized. Thermogravimetric analysis revealed that these compounds exhibit outstanding thermal stability and a tendency to sublime at a temperature exceeding around 350 °C without thermal decomposition. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to probe the frontier orbital energy levels of these compounds in THF solution. All three compounds undergo three quasi-reversible reductions with the first one leading to the formation of an anion radical, namely MPc(-.) , as confirmed by spectroelectrochemistry. The compounds studied were intrinsically resistive to oxidation, which indicates that they are very good electron acceptors (n-type materials). The HOMO-LUMO energy gaps (Eg ) of the three compounds determined by UV/Vis spectroscopy were relatively unaffected by the three-valent metals incorporated into the phthalocyanine macrocycle. Similarly, the energies of the HOMO (EHOMO ) and LUMO (ELUMO ) orbitals remained virtually unaffected by the three-valent metals in the perfluorophthalocyanine. Importantly, all the perfluorophthalocyanines studied possess LUMO levels between -4.76 and -4.85 eV, which makes their reduced forms resistant to electron trapping by O2 and H2 O. This property opens up the possibility for the fabrication of electronic devices operating under ambient conditions. All three compounds demonstrated very good photostability as solid thin films.

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Section: Electrochemistrysupporting

confidence: 56%

Section: Electrochemistrymentioning

confidence: 99%

Highly Thermostable, Non‐oxidizable Indium, Gallium, and Aluminium Perfluorophthalocyanines with n‐Type Character

Łapok

Obłoza

Nowakowska

2016

Chemistry A European J

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“…These spectral changes are associated with the p-anion radical formation, viz. Pc À C. [38,39] The appearance of aw eak band in the near-IR region of the spectrum upon first ring reduction wasp reviously reportedf or an umber of phthalocyanines. [38][39][40][41] However,i tw as usually observed at around9 50 nm.…”

Section: Electrochemical and Spectroelectrochemical Propertiesmentioning

confidence: 84%

“…Pc À C. [38,39] The appearance of aw eak band in the near-IR region of the spectrum upon first ring reduction wasp reviously reportedf or an umber of phthalocyanines. [38][39][40][41] However,i tw as usually observed at around9 50 nm. [38,39] The reduction observed for PdPcF 64 4 and PtPcF 64 5 is af ully reversible process because application of more positive potential recovers the originalspectrum in its initial shapeand intensity.Weobserved that the electrochromic behavior of PdPcF 64 4 and PtPcF 64 5 is extremelys ensitivet oe ven very small changes to the potential applied.…”

Section: Electrochemical and Spectroelectrochemical Propertiesmentioning

confidence: 84%

Near Infrared Phosphorescent, Non‐oxidizable Palladium and Platinum Perfluoro‐phthalocyanines

et al. 2016

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New Pd(II) and Pt(II) complexes with a highly electron-deficient ligand (H2 PcF64 ) were conveniently prepared in a three-step synthesis. This is the first time that the phosphorescence of phthalocyanines with a H2 PcF64 framework has been measured. Based on these measurements, the triplet-state energies (ET ) were directly determined. Transient absorption experiments revealed broad T1 →Tn absorption spanning from ca. 350 to ca. 1000 nm and allowed determination of the triplet-state lifetimes. Removal of the Pd or Pt from the perfluoro-phthalocyanine resulted in a significant increase of the triplet lifetime for H2 PcF64 . The very efficient intersystem crossing observed for both PdPcF64 and PtPcF64 leads to residual fluorescence and suppresses the fluorescence lifetimes to less than 50 ps. The absence of Pd and Pt in the perfluoro-phthalocyanine ligand, viz. H2 PcF64 , led to a recovery of fluorescence. Cyclic voltamperometry studies pointed to complete resistance of PdPcF64 and PtPcF64 to oxidation and very strong electron affinity, which rendered these materials very good electron acceptors (n-type materials). The presence of d-orbital metals such as Pd(II) and Pt(II) in the phthalocyanine ring stabilizes their reduced forms, as indicated by the spectroelectrochemical experiments. PdPcF64 and PtPcF64 easily sensitize singlet oxygen production with very high quantum yields. Both phthalocyanines presented resistance to photodegradation in the solid state under aerobic conditions and under intense irradiation.

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“…Ряд работ [9][10][11][12] посвящен исследованию электроки-нетических свойств фталоцианинатов металлов в нево-дных средах.…”

Section: Introductionunclassified

Physical-Chemical Properties of Modified Copper-Phthalocyanine and Its Aqueous Dispersions

Zuev¹,

Перевалов²,

Vinokurov³

et al. 2016

MHC

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Electrochemistry and spectroelectrochemistry of zirconium(IV) and hafnium(IV) phthalocyanines with b-diketone axial ligands

Abstract: Fourteen Zr

Cited by 18 publications

References 29 publications

Highly Thermostable, Non‐oxidizable Indium, Gallium, and Aluminium Perfluorophthalocyanines with n‐Type Character

Highly Thermostable, Non‐oxidizable Indium, Gallium, and Aluminium Perfluorophthalocyanines with n‐Type Character

Near Infrared Phosphorescent, Non‐oxidizable Palladium and Platinum Perfluoro‐phthalocyanines

Physical-Chemical Properties of Modified Copper-Phthalocyanine and Its Aqueous Dispersions

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