New charged cyclometalated iridium(III) complexes [Ir(ppy)2(L)](PF6) [ppy = 2-phenylpyridine; L = bis(pyrazol-1-yl)methane (for 1); L = bis(3,5-dimethylpyrazol-1-yl)methane (for 2)] were synthesized and their electrochemical and photophysical properties studied. These complexes with non-p-electron-conjugated ancillary chelates exhibit significantly blueshifted emission relative to those of commonly used derivatives with NN ancillary ligands such as bipyridine or phenanthroline. Both X-ray and theoretical analysis based on time-dependent density functional theory (TD-DFT) reveal that the binding of Ir to the bis(pyrazol-1-yl)methane ancillary ligand is much weaker than that to the phenylpyridine main ligand; the effect is enhanced in the excited state. As a result, the ancillary ligand does not participate in low-energy excitations and triplet emission, and the electronic transitions are concentrated on the main chromophoric ligands. The blueshift feature is attributed to emission originating from the main cyclometalated ligands, in contrast to emitters with the NN chromophoric ancillary ligand. In addition, complex 2 exhibits a one order of magnitude higher non-radiative decay rate than complex 1, which is attributed to the steric hindrance of the methyl groups that leads to a more loosely bound ancillary ligand.

The behavior toward oxygen sensing of nanocomposites made of the aluminum oxide-hydroxide nanostructured solid support (AP200/19) and neutral blue emitting cyclometalated iridium(III) complexes was studied. The results are compared with the same dyes immobilized in polystyrene films. Since the photoluminescence of the complexes is totally quenched for oxygen concentrations just over 10%, these systems using the blue region of the visible spectrum are promising for oxygen detection at low concentration. In particular, dyes supported into the AP200/19 provide the best sensitivity to oxygen concentration, with the possibility to detect oxygen below 1% O2 in gas (0.01 bar).

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A library of emission spectra of 90 bis-cyclometallated iridium complexes has been obtained using a simple combinatorial approach performed at room temperature. Trends in emission maxima are rationalized using Hammett parameters and invoking inter ligand energy transfer (ILET) processes. The screening approach allowed us to observe trends in the broadness of emission spectra opening the way for a rational approach to the engineering of the emission colour purity at a molecular level. Finally limitations to the screening strategy are discussed using a case study that involves two different monodentate ligands.

Novel organic sensitizers comprising donor; electron-conducting, and anchoring groups were engineered at molecular level and synthesized. The functionalized unsymmetrical organic sensitizers 3-{5-[ N,N -Bis(9,9-dimethylfluorene-2-yl)phenyl]-thiophene-2-yl}-2-cyano-acrylic acid (JK-1) and 3-{5’-[N,N-Bis(9,9-dimethylfluorene-2-yl)phenyl]-2,2’-bithiophene-5-yl}-2-cyano-acrylic acid (JK-2), upon anchoring onto TiO2 film exhibit unprecedented incident photon to current conversion efficiency 91 %. The photovoltaic data using an electrolyte having composition of 0.6M M-methyl-N-butyl imidiazolium iodide, 0.04 M iodine, 0.025 M LiI, 0.05M guanidinium thiocyanate and 0.28 M tert.butylpyridine in 15/85 (v/v) mixture of valeronitrile and acetonitrile revealed a short circuit photocurrent density of 14.0 mA/cm2, an open circuit voltage of 753 mV and a fill factor of 0.76, corresponding to an overall conversion efficiency of 8.01 % under standard AM 1.5

A sensitive matter: New sensitizers based on cyclometallated iridium (III) complexes have been studied. Despite poor absorption properties, efficiencies up to 2.5 % were observed. It was seen that poor light-harvesting properties of the dyes are the main reasons for those efficiencies, which may be improved with better light-absorbing ligands. Electron-dynamic investigations show that very fast processes are taking place. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

A highly efficient heteroleptic ruthenium (II) complex cis-di(thiocyanato)(4,4′-dicarboxylic acid-2,2′-bipyridine)(4,4′-di-(2-(4-ditolylamine phenyl)ethenyl)-2,2′-bipyridine) ruthenium (II) (IJ-1) was synthesized and characterized, which when anchored on nanocrystalline TiO2 films exhibited high power conversion efficiency, 10.3%, and incident photon to electron conversion efficiency, 87%.

Preparation of a triisocyanide ligand, 1,3,5-tris[(4-isocyano-3,5-diisoproyl-phenyl)ethynyl]benzene (5), is presented. Ligand 5 is obtained in three steps in 76% overall yield. Reaction of 5 with (eta5-Cp*)Rh(Cabs,s')(Cabs,s'= 1,2-S2C2B10H10-S,S') produced the rhodadithiolene adduct [[(eta5-Cp*)Rh(Cabs,s')(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (6). Ligand 5 reacts with Cr(CO)5(THF) to give the triisocyanide complex [[Cr(CO)5(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (8) and with [AuCl(SMe2)] to give the triisocyanide complex [[AuCl(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (9). As revealed by a single-crystal X-ray diffraction study, the C(9)-N(3)-C(61) angle of 5.9 degrees of trichromium complex 8 occurs in the plane of the bridge and the gold center has a slightly bent linear configuration with a Cl(1)-Au(1)-C(21) angle of 175.4(4) degrees . The rhenation and platination of 5 employing [Re(bpy)(CO)3(AN)]PF6 (AN= acetonitrile) and [(CwedgeNwedgeN)PtCl] ((HCwedgeNwedgeN)= 6-phenyl-2,2'-bipyridine) yielded the luminescent Re(I) and Pt(II) complexes. Full characterization includes structural study of complexes 2, 8, and 9.

We have studied photovoltaic performances based on the newly synthesized dyes. Under standard AM 1.5 sunlight, the dye D20 gave a short-circuit photocurrent density of 13.31mA/cm2, an open-circuit voltage of 0.64V, and a fill factor of 0.68, corresponding to an overall conversion efficiency of 5.81%.

New organic dyes composed of the benzo[b]furan donor, thiophene-conjugated bridge, and cyano acrylic acid acceptor have been newly synthesized through the one-pot coupling cyclization key step. Nanocrystalline TiO2 dye-sensitized solar cell was fabricated using this dye. A solar-to-electric conversion efficiency of 6.65% and 4.70% is achieved with 1 and 2, respectively.

Rigid spacer-chelator with the framework of 3 has been prepared. Building units with two parallel coordination sites such as salen and oxazoline units have also been synthesized. The spacer-chelators, 11 and 15, readily self-assembled with metal complexes such as Zn++ and Co++ to form molecular rectangles. The overall dimensions of the rectangles, 13 and 17, are 6.2 angstrom x 23.5 angstrom. The characterization of the supramolecules by NMR, mass spectroscopy, and X-ray crystal structures is also reported. (c) 2006 Elsevier B.V. All rights reserved.

A novel class of diarylethene derivatives, (diaryl = N-7-azaindolylpheny, naphthylphenylamine, m-tolylphenylamine, ethene = perfluorocyclopentene) were synthesized and experiments were performed their usage in organic light-emitting diodes (OLEDs). Compound 3 , 1,2-Bis{4-[(phenyl)(m-tolyl)amino]biphenyl}-3,3,4,4,5,5-hexafluorocyclopentene, exhibits a strong green emission in both a solution and a thin film at similar to 540 nm. The device with 3 as an emitting material (structure: ITO/TPD/3/Alq 3 (q = tris-(8-hydroxyquinolinolate))/Al:Li) shows high quantum efficiency with 7677 cd/m(2) at similar to 13 V.

A novel series of blue emitting silylene-spaced diphenylanthracene derivatives have been synthesized and characterized. The rhodium-catalyzed hydrosilylation of bis[4-(dimethylsilyl)phenyl]anthracene 3-4 yielded stable 9,10-disubstituted (E)-divinylsilylenediphenylanthracene products 7-10 and salt elimination reaction of bis[4-(chlorodimethylsilyl)phenyllanthracene 5-6 gave 9,10-disubstituted disilyldiphenylanthracene compounds 11-14. They are fluorescent in the blue region with good quantum efficiencies. The rhodium-catalyzed polyaddition including 2-tert-butyl-9,10-bis[4-(dimethylsilyl)phenyl]anthracene (4) afforded the nonconjugated copolymer 15. (c) 2006 Elsevier B.V. All rights reserved.

Two diarylethene trimers bridged by ethenyl and ethynyl groups were synthesized and their photochromic behaviors were examined. Upon irradiation of the trimers 2 and 4 with UV light, one–three photoinduced cyclization reactions occur. Each isomer was isolated and analyzed by 1H NMR spectrum. The quantum yield of 2 and 4 is 0.52 and 0.311, respectively.

Two macrocycles bearing four dithienylethene units were synthesized. Upon irradiation of the macrocycles 5 and 6 with ultraviolet light, only one or two photo-induced cyclization reaction occurs. Each isomers were isolated and analyzed by 1H NMR spectrum. The quantum yield of 5 and 6 are 0.58 and 0.64, respectively. The high value is due to the presence of enforced antiparallel conformation in the macrocycles 5 and 6.

ChemInformVolume 36, Issue 35 Isocyclic Compounds Hydrostannation of Diyne and Triyne π-Electron Bridges: Efficient Stille Cross-Coupling of 1,3,5-Tris[(E)-2-(tributylstannyl)vinyl]benzene. Il Jung, Il Jung Dep. Chem., Korea Univ., Chungnam 339-700, S. KoreaSearch for more papers by this authorTaegweon Lee, Taegweon Lee Dep. Chem., Korea Univ., Chungnam 339-700, S. KoreaSearch for more papers by this authorSang Ook Kang, Sang Ook Kang Dep. Chem., Korea Univ., Chungnam 339-700, S. KoreaSearch for more papers by this authorJaejung Ko, Jaejung Ko Dep. Chem., Korea Univ., Chungnam 339-700, S. KoreaSearch for more papers by this author Il Jung, Il Jung Dep. Chem., Korea Univ., Chungnam 339-700, S. KoreaSearch for more papers by this authorTaegweon Lee, Taegweon Lee Dep. Chem., Korea Univ., Chungnam 339-700, S. KoreaSearch for more papers by this authorSang Ook Kang, Sang Ook Kang Dep. Chem., Korea Univ., Chungnam 339-700, S. KoreaSearch for more papers by this authorJaejung Ko, Jaejung Ko Dep. Chem., Korea Univ., Chungnam 339-700, S. KoreaSearch for more papers by this author First published: 02 August 2005 https://doi.org/10.1002/chin.200535110Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References Il Jung, Taegweon Lee, Sang Ook Kang, Jaejung Ko, Hydrostannation of Diyne and Triyne π-Electron Bridges: Efficient Stille Cross-Coupling of 1,3,5-Tris[(E)-2-(tributylstannyl)vinyl]benzene., Synthesis, 2005, 986–992. CASWeb of Science®Google Scholar Volume36, Issue35August 30, 2005 ReferencesRelatedInformation

The facile hydrostannation of diynes and triynes with tributyltin hydride was achieved. The hydrostannation product readily underwent the Stille cross-coupling reaction with a variety of aryl bromides. The copper-mediatedStille cross-coupling of 1,3,5-tris[(E)-2-(tributylstannyl)vinyl]benzene with (E)-β-iodostyrene afforded the conjugated diene.

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The Rh(I)-catalyzed hydroboration of a variety of aromatic diynes and a triyne afforded bis(boryl)- and tris(boryl)vinyl products. The hydroboration products under-went Suzuki cross-coupling reactions with a variety of substrates containing chromophore units to give fluorescent dye-substituted products. The hydroboration product also reacted with dibromoarenes to afford an oligomer with a vinylene unit along the oligomer backbone.