Synthesis and Properties of Copper(II) Phthalocyanines with Monoazacrown and Crown Ethers as Peripheral Substituents

Abstract

<jats:p> Soluble and less soluble phthalocyaninatocopper(II) derivatives (4a and 4b) were prepared from the corresponding 7-[(4′-benzo-15-crown-5)oyl]-15, 16-dibromo-2,3,6,7,8,9,11,12-octahydro-5H-benzo[e]-[1,4,10,13,7] tetraoxaazacyclopentadecine (3a) and 7-(2′-tosylaminoethyl)-15, 16-dibromo-2,3,6,7,8,9,11, 12-octahydro-5H-benzo[e]-[1,4,10,13,7] tetraoxaazacyclopentadecine (3b) and CuCN in pyridine. A less soluble novel multifunctionalized scorpiand macrocycle-substituted phthalocyanine (4c) in which an NH <jats:sub>2</jats:sub> CH <jats:sub>2</jats:sub> CH <jats:sub>2</jats:sub>— chain is appended to a monoazacrown ether ring was obtained by detosylation of 4b with concentrated sulfuric acid. </jats:p>

Functional fluoro substituted tetrakis-metallophthalocyanines: Synthesis, spectroscopy, electrochemistry and spectroelectrochemistry

“…), and electron-donating (-NH 2 , Ar-S-, RO-, etc.) bulky or long chain groups [11][12][13][14][15][16]. Metal phthalocyanines bearing fluorine atoms are currently receiving a great deal of attention due to their high thermal and chemical stability; they also possess interesting electron-transporting characteristics [17].…”

Microwave-assisted synthesis and characterization of novel metal-free and metallophthalocyanines containing four 14-membered tetraaza macrocycles

“…These Q band absorptions broad and non-symmetric because of aggregation [32,33]. Also an increase in the concentration leads to aggregation which is easily monitored by the position of the Q-band which is shifted to shorter wavelengths, and to a decrease in molar absorption coefficient [34][35][36]. The presence of strong absorption bands in 6 in the near UV region at k max = 431, 344, 321 and 288 nm also shows Soret region B bands which have been ascribed to the deeper p-p * levels of LUMO transitions.…”

Peripheral Metal-Ion Binding to Tris(thia−oxo crown) Porphyrazines

“…Metal-ion binding to 1b(H 2 ) and 1c(Co) elicits extensive absorbance changes in the visible-to-near-IR region. Importantly, these changes are intrinsic to the pz's themselves and will occur when the pz's are surface confined, unlike the optical changes upon metal binding to pc crowns, [40][41][42][43][44][45][46][47][48][49][50][51] which are dominated by aggregation. Further, of the optical experiments, Figures 1-3, three of the four titration curves are well described by a 1:1 binding isotherm, although all four show nonisosbesticity, which indicates that more than one ion binds and that there are intermediate stages in the process.…”