Potential Aluminium(III)- and Gallium(III)-selective Optical Sensors Based on Porphyrazines

Abstract

Porphyrazines possessing non-coordinating alkyl (propyl) and aralkyl (4-tert-butylphenyl) groups in the periphery were studied as optical sensors for a set of mono-, di-and trivalent cations. Investigated porphyrazines in the UV-Vis monitored titrations revealed significant responses towards aluminium and gallium cations, unlike other metal ions studied. Additionally, porphyrazine possessing 4-tert-butylphenyl peripheral substituents showed sensor property towards ruthenium cation and was chosen for further investigation. The presence of isosbestic points in absorption spectra for its titration with aluminium, gallium and ruthenium cations, accompanied by a linear Benesi-Hildebrand plot, proved complex formation. The continuous variation method was used to determine binding stoichiometry in 1:1 porphyrazine-metal ratio. X-Ray studies and density functional theory calculations were employed to investigate octa(4-tert-butylphenyl)-porphyrazine structure. The results helped to explain the observed selectivity towards certain ions. Interaction between ion and porphyrazine meso nitrogen in a Lewis acid-Lewis base manner is proposed.

Peripheral Arylation of Subporphyrazines

“…Notably, the redshift of the SubPz Q-band is quantitatively comparable to that produced upon peripheral arylation of porphyrazines (Pz). [15] The charge-transfer band, however, is exceedingly more intense in the SubPz class than in the Pz series. [15] Importantly, the electronic properties of hexaaryl-SubPzs can be fine-tuned by introducing groups of distinct nature at the para positions of the peripheral aryl groups (see Figure 1 and Table 1).…”

“…[15] The charge-transfer band, however, is exceedingly more intense in the SubPz class than in the Pz series. [15] Importantly, the electronic properties of hexaaryl-SubPzs can be fine-tuned by introducing groups of distinct nature at the para positions of the peripheral aryl groups (see Figure 1 and Table 1). Here, the effects are different depending on the electron donor or acceptor abilities of the para substituents.…”

Dendrimeric Sulfanyl Porphyrazines: Synthesis, Physico‐Chemical Characterization, and Biological Activity for Potential Applications in Photodynamic Therapy

“…The spectroscopic, photochemical, and electrochemical properties of Pzs have been studied widely. These properties render them suitable for potential applications in photodynamic therapy (PDT) and photodynamic diagnosis (PDD) as photosensitizers, in chemical catalysis, and in analytical chemistry as sensors . Porphyrazines that contain sulfanyl substituents reveal good solubility in common organic solvents and significant photocytotoxicities .…”

“…[1] The spectro-scopic,p hotochemical, and electrochemical properties of Pzs have been studied widely.T hese properties render them suitable for potential applications in photodynamic therapy (PDT) and photodynamic diagnosis (PDD) as photosensitizers, in chemicalc atalysis, and in analytical chemistry as sensors. [2][3][4][5] Porphyrazines that contain sulfanyl substituents revealg ood solubility in common organic solvents and significant photocytotoxicities. [6][7][8][9] Many years of research on sulfanyl porphyrazines led to the expansion of their periphery with various groups;f or example, ether/thioether, [10,11] calixarene, [12] (tetrathiafulvalene)sulfanylethyl, [13] 2'-(4-pyridoxy)ethyl, [14] 1-naphthylmethyl, [8] 2'-(ferrocenecarboxy)ethyl, [15] and 4-(4-nitroimidazol-1-yl)butyl.…”

The Influence of Peripheral Substituent Modification on PV, MnIII, and MnV(O) Corrolazines: X-ray Crystallography, Electrochemical and Spectroscopic Properties, and HAT and OAT Reactivities

“…These shifts are consistent with protonation of a meso -nitrogen atom on the corrolazine ring. 23,32,56,62–64 Layering of a toluene solution of [TBP 8 CzH 4 ][BArF] with n -heptane gave dark-colored crystals after one week. The crystal structure of the monoprotonated metal-free [TBP 8 CzH 4 ][BArF] is shown in Figure 3.…”