Photosensitizing Properties of Some Rhenium(I) Tricarbonyl Diimine Complexes

Lam, Lillian Sze Man; Chan, Wai Kin

doi:10.1002/1439-7641(20010417)2:4<252::aid-cphc252>3.0.co;2-w

“…In this paper, we report the spectroscopic ellipsometry study of PC doped with triphenylamine and another chlorotricarbonyl rhenium complex based on 1,4-diazabutadiene ligand. The synthesis [8] and detailed study of photogeneration of this complex doped in PC will be reported elsewhere.…”

Section: Introductionmentioning

confidence: 99%

Optical properties of doped polycarbonate layers

Djurišić

¹

,

Guo

²

,

Li

³

et al. 2001

Optics Communications

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“…It was demonstrated previously that some polymeric rhenium complexes were able to act as both electron and hole carriers. [48][49][50] The electrons were transported by hopping between the diimine ligands, which exhibited modest electron-carrier mobility. After evaporation of the aluminum electrode, the multilayered devices were irradiated with simulated AM 1.5 solar light.…”

mentioning

confidence: 99%

Layer‐by‐Layer Deposition of Rhenium‐Containing Hyperbranched Polymers and Fabrication of Photovoltaic Cells

Tse

¹

,

Man

²

,

Cheng

³

et al. 2006

Chemistry A European J

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Multilayer thin films were prepared by the layer‐by‐layer (LBL) deposition method using a rhenium‐containing hyperbranched polymer and poly[2‐(3‐thienyl)ethoxy‐4‐butylsulfonate] (PTEBS). The radii of gyration of the hyperbranched polymer in solutions with different salt concentrations were measured by laser light scattering. A significant decrease in molecular size was observed when sodium trifluoromethanesulfonate was used as the electrolyte. The conditions of preparing the multilayer thin films by LBL deposition were studied. The growth of the multilayer films was monitored by absorption spectroscopy and spectroscopic ellipsometry, and the surface morphologies of the resulting films were studied by atomic force microscopy. When the pH of a PTEBS solution was kept at 6 and in the presence of salt, polymer films with maximum thickness were obtained. The multilayer films were also fabricated into photovoltaic cells and their photocurrent responses were measured upon irradiation with simulated air mass (AM) 1.5 solar light. The open‐circuit voltage, short‐circuit current, fill factor, and power conversion efficiency of the devices were 1.2 V, 27.1 μ A cm−2, 0.19, and 6.1×10−3 %, respectively. The high open‐circuit voltage was attributed to the difference in the HOMO level of the PTEBS donor and the LUMO level of the hyperbranched polymer acceptor. A plot of incident photon‐to‐electron conversion efficiency versus wavelength also suggests that the PTEBS/hyperbranched polymer junction is involved in the photosensitization process, in which a maximum was observed at approximately 420 nm. The relatively high capacitance, determined from the measured photocurrent rise and decay profiles, can be attributed to the presence of large counter anions in the polymer film.

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Rhenium: Organometallic Chemistry

Romão

¹

2005

Encyclopedia of Inorganic Chemistry

2

0

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The organometallic chemistry of Rhenium spans 11 oxidation states. Since many ligands stabilize several oxidation states, this chemistry is described by ligand type. Re‐Re multiple bonded organometallic complexes, Polynuclear organometallic complexes, and Bioorganometallic Chemistry, uncoverable in this fashion, are treated separately. The CO ligand dominates the chemistry of the lower oxidation states (Re −III to Re II ) most of which is derived from Re 2 (CO) 10 and the consequences of the rupture of its Re‐Re bond. [Re(CO) 5 ] • , [Re(CO) 5 ] − and Re(CO) 5 X are the most important products of Re‐Re homolysis, reduction and oxidation, respectively, and originate a vast chemistry. [ReX x (CO) y L z ] is the largest family of organorhenium complexes. The luminescent fac ‐[ReX(CO) 3 L 2 ] molecules assume high practical relevance in photoresponsive materials and sensors. Polyhydrides [ReH x L y ] lose H 2 upon thermal, photochemical or oxidative activation promoting alkane dehydrogenation. The abundant [Re(CO) x H y ] clusters are important building blocs for catalysts and materials. [ReH(CO) 4 ] n are analogues of cycloalkanes. Mononuclear homoleptic alkyls and aryls of Re in high oxidation states are limited to ReMe 6 and [Re(2‐MeC 6 H 4 ) 4 ]. Instead, carbenes and carbynes, as the remarkable [Re(≡CCMe 3 )(=CHCMe 3 )(CH 2 CMe 3 ) 2 ], are common. Re VII oxo and imido complexes also originate carbene/carbyne complexes active in olefin metathesis catalysis. ReO 3 Me (MTO) is a uniquely versatile catalyst in a wide variety of oxidation and O transfer catalysis. ReO 2 Me derivatives are active catalysts namely in aldehyde olefination. η 2 ‐, η 3 ‐, η 4 ‐ (dienes), η 6 ‐ (arenes) and η 7 ‐ (cycloheptatrienyl) ligands play a limited role in the organorhenium chemistry. Exceptional is, however, the activation of η 2 ‐arenes by Re I complexes. The dearomatized benzene ring in TpRe(CO)(MeIm)(η 2 ‐C 6 H 6 ) reacts as a diene. Unusual alkyne complexes appear in Re III and Re V oxides, e.g. ReR(O)(η 2 ‐RCCR) (R = H, alkyl). [Cp'Re(CO) 2 (η 3 ‐propargyl)] + complexes reveal a fascinating series of structural transformations and rearrangements. The cyclopentadienyl ligand (η 5 ‐C 5 R 5 = Cp’) shapes the large families of complexes of the fragments Cp’ 2 Re (rhenocene) Cp'Re(CO) 2 , [Cp'Re(NO)(PPh 3 )] + and Cp'ReO x X y . Hydrocarbyl transformations at these fragments and the understanding of the stereochemical control in enantioselective transformations of ligands bound to the chiral‐at‐metal fragment [Cp'Re(NO)(PPh 3 )] + are of outstanding relevance. Isoelectronic neutral or negative 6 e donors may enhance these transformations and support new ones. [Cp*Re(CO) 2 ] 2 and [Re(≡CCMe 3 )(OCMe 3 ) 2 ] 2 are rare examples of unsupported dimers of 16e fragments. Re isocyanide and nitrosyl complexes follow most of the structural and chemical patterns found for the carbonyl ligand. However, recent findings revealed that the participation of the O atom of the NO ligand in H bonding may lead to unexpected reactivity. Polynuclear Re complexes span a bewildering variety of synthetic methods and structural motifs. The ultimate rationale for their study is cooperative catalysis, as modelled in alkene hydrogenation with a Re/Pt binuclear complex and applied in petroleum refining with Pt x Re y clusters. Bioorganometallic chemistry is rapidly evolving into practical medical applications in diagnostics and therapy. Stable Re(CO) 3 fragments decorated with biologically active molecules are able to target Re compounds to specific tissues/organs. New synthetic methods have been developed for the synthesis of the required molecules in aqueous solution, avoiding the use of CO gas and classical high pressure synthesis.

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Photosensitizing Properties of Some Rhenium(I) Tricarbonyl Diimine Complexes

Cited by 22 publications

References 29 publications

Optical properties of doped polycarbonate layers

Optical properties of doped polycarbonate layers

Layer‐by‐Layer Deposition of Rhenium‐Containing Hyperbranched Polymers and Fabrication of Photovoltaic Cells

Rhenium: Organometallic Chemistry

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