Triple-decker Complexes (triple-decker + complex)

Distribution by Scientific Domains


Selected Abstracts


Synthesis and Characterization of Mixed Phthalocyaninato and meso -Tetrakis(4-chlorophenyl)porphyrinato Triple-Decker Complexes , Revealing the Origin of Their Electronic Absorptions

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2004
Xuan Sun
Abstract Two series of mixed phthalocyaninato and porphyrinato rare earth(III) triple-decker complexes [M2(Pc)(TClPP)2] (1a,10a) and [M2(Pc)2(TClPP)] (1b,11b) [M = Y, La,Er except Ce and Pm; Pc = phthalocyaninate; TClPP = tetrakis(4-chlorophenyl)porphyrinate] have been prepared by treating the half-sandwich complexes [M(TClPP)(acac)] (acac = acetylacetonate), generated in situ from [M(acac)3]·nH2O and H2(TClPP), with Li2(Pc). All the triple-decker complexes have been characterized by a wide range of spectroscopic and electrochemical methods. The molecular structures of [M2(Pc)(TClPP)2] (M = Y, Ho) have also been determined, and show a symmetrical disposition of ligands, with two outer domed TClPP and one inner Pc rings. A systematic investigation of the optical and electrochemical data of these complexes has revealed the nature of the HOMO and LUMO, as well as the origin of the electronic absorptions of these triple-decker complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]


NMR-based analysis of structure of heteroleptic triple-decker (phthalocyaninato) (porphyrinato) lanthanides in solutions

MAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2010
Kirill P. Birin
Abstract A novel approach for the structural analysis of heteroleptic triple-decker (porphyrinato)(phthalocyaninato) lanthanides(III) in solutions is developed. The developed approach consists in molecular mechanics (MM+) optimization of the geometry of the complex taking into account the lanthanide-induced shift (LIS) datasets. LISs of the resonance peaks in 1H NMR spectra of a series of symmetric complexes [An4P]Ln[(15C5)4Pc]Ln[An4P], where An4P2, is 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato-dianion, [(15C5)4Pc]2, is 2,3,9,10,16,17,24,25-tetrakis(15-crown-5)phthalocyaninato-dianion and Ln = La, Ce, Pr, Nd, Sm, Eu, are analyzed. Analysis of LISs showed two sets of protons in the molecule with opposite signs of shift. Two-nuclei analysis of LISs testifies isostructurality of the whole series of investigated complexes in solution despite contraction of the lanthanide ions. Model-free separation of contact and dipolar contributions of LISs was performed with one-nucleus technique and did not show changes in contact and dipolar terms within the investigated series. MM+ optimization of the molecular structure allowed the interpretation of features of LIS for each particular group of protons. Parameterization of MM + -optimized model of molecule with values of structure-dependent dipolar contributions of LIS allows the development of the precise structural model of the triple-decker complex in solution. This approach allows the determination of the geometry and structure of the sandwich macrocyclic tetrapyrrolic complexes together with conformational analysis of flexible peripheral substituents in solutions. The developed method can be applied with minor modifications for the determination of structural parameters of other types of lanthanides(III) complexes with tetrapyrrolic ligands and also supramolecular systems based on them. Copyright © 2010 John Wiley & Sons, Ltd. [source]


Synthesis, Characterization and OFET Properties of Amphiphilic Mixed (Phthalocyaninato)(porphyrinato)europium(III) Complexes

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2009
Pan Ma
Abstract Amphiphilic mixed (phthalocyaninato)(porphyrinato)europium(III) triple-decker complexes Eu2[Pc(15C5)4]2[T(C10H21)4P] (1) and Eu2[Pc(15C5)4]2[TPOPP] (2) [H2Pc(15C5)4 = 2,3,9,10,16,17,23,24-tetrakis(15-crown-5)phthalocyanine; H2T(C10H21)4P = meso -5,10,15,20-tetra- n -decylporphyrin, H2TPOPP = meso -5,10,15,20-tetrakis(4-pentyloxyphenyl)porphyrin] were designed and synthesized by the raise-by-one-story method. These novel sandwich triple-decker complexes were characterized by a wide range of spectroscopic methods, and they were also electrochemically studied. Highly ordered films were fabricated by the Langmuir,Blodgett (LB) technique into organic field-effect transistors (OFETs). The devices display good OFET performance with a carrier mobility in the range 0.03,0.78 cm2,V,1,s,1. As expected, the devices show a low threshold voltage range from ,1.19 to ,4.34 V. The mobility of compound 1 reaches 0.78 cm2,V,1,s,1, which is the highest value so far achieved for LB film-based OFETs, as a result of the narrow energy gap (1.04 eV) of this compound.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]


Triple-Decker Transition-Metal Complexes (CnHn)M(B6C)M(CnHn) (M = Fe, Ru, Mn, Re; n = 5, 6) Containing Planar Hexacoordinate Carbon Atoms

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2006
Si-Dian Li
Abstract A density functional theory investigation is presented in this work on a new class of triple-decker complexes (CnHn)M(B6X)M(CnHn) (M = Fe, Ru, Mn, Re; X = B, C, N; n = 5, 6) containing almost perfect planar hexacoordinate carbon atoms and other planar hexacoordinate nonmetals at the centers of the B6X middle-deckers. Effective d,, coordination interactions between the partially filled 3d orbitals of the transition-metal center and the delocalized , orbitals of the three parallel ligands maintain the stabilities of these triple-decker complexes. The strong IR absorption peaks of (CnHn)M(B6X)M(CnHn) complexes mainly originate from the in-plane and off-plane vibrations of their planar hexacoordinate nonmetal centers. The results obtained in this work provide a possible new approach to characterize planar hexacoordinate carbon-containing systems in future experiments and expand the structural domain of transition-metal complexes by introducing inorganic B6X middle-deckers into traditional sandwich-type structures. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]


Synthesis and Characterization of Mixed Phthalocyaninato and meso -Tetrakis(4-chlorophenyl)porphyrinato Triple-Decker Complexes , Revealing the Origin of Their Electronic Absorptions

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2004
Xuan Sun
Abstract Two series of mixed phthalocyaninato and porphyrinato rare earth(III) triple-decker complexes [M2(Pc)(TClPP)2] (1a,10a) and [M2(Pc)2(TClPP)] (1b,11b) [M = Y, La,Er except Ce and Pm; Pc = phthalocyaninate; TClPP = tetrakis(4-chlorophenyl)porphyrinate] have been prepared by treating the half-sandwich complexes [M(TClPP)(acac)] (acac = acetylacetonate), generated in situ from [M(acac)3]·nH2O and H2(TClPP), with Li2(Pc). All the triple-decker complexes have been characterized by a wide range of spectroscopic and electrochemical methods. The molecular structures of [M2(Pc)(TClPP)2] (M = Y, Ho) have also been determined, and show a symmetrical disposition of ligands, with two outer domed TClPP and one inner Pc rings. A systematic investigation of the optical and electrochemical data of these complexes has revealed the nature of the HOMO and LUMO, as well as the origin of the electronic absorptions of these triple-decker complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]