Photophysical and photochemical properties of non-peripheral butoxy-substituted phthalocyanines with absorption in NIR range

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Effect of the [2-(diphenylphosphorylmethoxy)phenyl]diphenylphosphine oxide derivative structures on the extraction and ion-selective properties toward rare-earth elements

The effect of structures of the derivatives of [2-(diphenylphosphorylmethoxy)phenyl]-diphenylphosphine oxide (L¹) on the complexation properties toward rare-earth elements (REE) was studied. A new structural analogue of L¹, isopropyl 2-(diphenylphosphorylmethoxy)benzoate (L³), was synthesized. The extraction of REE by the carboxylated podand L³ in a 1,1,7-trihydrododecafluoroheptanol—water system with the HNO₃ concentration varied in a range from 1 to 6 mol L^?1 was studied. The stability constants of the neodymium(iii) and erbium(iii) nitrate complexes with L³ and 1-(methoxydiphenylphosphoryl)-2-diphenylphosphoryl-4-ethylbenzene (L²) and of lutetium(iii) nitrate and chloride complexes with L² in 1,1,7-trihydrododecafluorheptanol were determined. The properties of the membranes of the ion-selective electrodes based on L¹, L², and L³ toward REE cations were tested. The crystal structures of L³ and [NdL³(NO₃)₃(DMSO)₂] were determined by X-ray diffraction analysis.

     

Crown-substituted Sc(III) phthalocyaninates: Synthesis and spectral properties

The scandium(III) complexes with tetra(15-crown-5)phthalocyanine [Sc(R₄Pc)₂]^·0 (I) and Sc(R₄Pc) · OAc (II) have been synthesized by condensation of Sc³⁺ with phthalocyanine H₂R₄Pc (4,5,4′,5′,4″,5″,4?,5?-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyanine). Compounds I and II have been characterized by spectral methods: electronic absorption spectroscopy, MALDI-TOF MS, IR spectroscopy, and ¹H NMR. The redox properties of I and the photoluminescent properties of II have been studied.     

Photorefractive IR-range composites on the basis of poly(vinyl carbazole) and ruthenium (II) tetra-15-crown-5-phthalocyanines

The photoelectric sensitivity and photorefractive properties at 1064 nm of composites consisting of poly(vinyl carbazole) (PVC), complexes of ruthenium(II) with tetra-15-crown-5-phthalocyanine and axially coordinated CO and CH₃OH molecules (R₄Pc)Ru(CO)(CH₃OH), R₄Pc^2? is tetrakis-(1,4,7,10,13-pentaoxatridecamethylene)phthalocyaninate ion in the presence and absence of ferrocene were studied. The nature of the optical absorption within the near IR region in composites prepared from PVC and (R₄Pc)Ru(TED)₂ (TED is triethylenediamine) and (R₄Pc)Ru(CO)(CH₃OH) is discussed. It was established that the photoelectric, non-linear optical, and photorefractive properties of the polymer composite are determined by supramolecular ensemble composed of Ru(II) crown-phthalocyanines.     

Ion-selective properties of 1,8-bis [2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H4L3), synthesis and vibrational spectra of copper and zinc complexes with H4L3, and crystal and molecular structure of [Cu(H4L3)(H2O)3][(H2L3)(H2O)]

The ion-selective properties of 1,8-bis[2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H₄L³) have been studied and its potentiometric selectivity coefficients have been determined. New complexes [Cu(H₄L³)(H₂O)₃][(H₂L³)(H₂O)] (I) and Zn(H₄L³)(H₂L³) · 3H₂O, and Cu(H₂L³) · 2(H₂O) have been synthesized and characterized. The crystal and molecular structure of I has been determined by X-ray crystallography and vibrational spectroscopy. The crystals are monoclinic, a = 10.279(5) Å, b = 26.532(13) Å, c = 8.399(4) Å, β = 99.270(8)°, V = 2260.8(7) ų, Z = 2, space group Cm, R = 0.0347 for 4325 reflections with I > 2σ(I). Ionic compound I is composed of the [Cu(H₄L³)(H₂O)₃]²⁺ complex cations and [(H₂L³)(H₂O)]^2? anions. In the cation, the Cu²⁺ cation located in the m plane is bound to a tetragonal pyramidal (TP) array. The equatorial plane of the TP is formed by two phosphoryl oxygen atoms of the podand (Cu(1)-O, 1.921(2) Å) and two O atoms of two water molecules (av. Cu(1)-O, 1.981(3) Å). The third water molecule is at the axial vertex of the TP at a considerably larger distance (Cu(1)-O, 2.139(3) Å). The anion is of the host-guest type. The host is the deprotonated podand (H₂L³)^2?, and the guest is the water molecule. The latter is bound to the terminal hydroxyl groups of two phosphoryl groups of the podand by two acceptor hydrogen bonds and to two central ether oxygen atoms of the (H₂L³)^2? anion by one donor bifurcated hydrogen bond. The cations and anions in the structure are linked by hydrogen bonds to form chains parallel to the c axis.