1,721,070 research outputs found
Analysis of the role of the pH in the anchoring of alkylphosphonic acid on a TiO2 surface: A DFTB study
No full textExcited-State Engineering in Heteroleptic Ionic Iridium(III) Complexes
Full text linkIridium(III) complexes have assumed a prominent role in the areas of photochemistry and photophysics due to the peculiar properties of both the metal itself and the ligand environment that can be assembled around it. Ir(III) is larger, heavier, and bears a higher ionic charge than its analogue and widely used d6 ions such as Fe(II) and Ru(II). Accordingly, its complexes exhibit wider ligand-field d-d orbital splitting with electronic levels centered on the metal, typically nonemissive and photodissociative, not playing a relevant role in excited-state deactivations. In other words, iridium complexes are typically more stable and/or more emissive than Fe(II) and Ru(II) systems. Additionally, the particularly strong heavy-atom effect of iridium promotes singlet-triplet transitions, with characteristic absorption features in the UV-vis and relatively short excited-state lifetimes of emissive triplet levels. Ir(III) is also a platform for anchoring ligands of rather different sorts. Its versatile chemistry includes not only coordination with classic N∧N neutral ligands but also the binding of negatively charged chelators, typically having a cyclometalating C∧N anchor. The carbon-metal bond in these systems has some degree of covalent character, but this does not preclude a localized description of the excited states of the related complexes, which can be designated as metal-centered (MC), ligand-centered (LC), or charge transfer (CT), allowing a simplified description of electronic and photophysical properties. The possibility of binding different types of ligands and making heteroleptic complexes is a formidable tool for finely tuning the nature and energy of the lowest electronic excited state of cationic Ir(III) complexes by ligand design. Herein we give an account of our work on several families of iridium complexes typically equipped with two cyclometalating bidentate ligands (C∧N), in combination with mono or bidentate "ancillary"ligands with N∧N, C∧N, and C∧C motifs. We have explored new synthesis routes for both cyclometalating and ancillary ligands, obtaining primarily cationic complexes but also some neutral or even negatively charged systems. In the domain of the ancillary ligands, we have explored isocyanides, carbenes, mesoionic triazolylidenes, and bis-tetrazolic ligands. For the cyclometalating moiety, we have investigated carbene, mesoionic triazolylidene, and tetrazolic systems. Key results of our work include new strategies to modify both cyclometalating and ancillary ligands by relocating ionic charges, the determination of new factors affecting the stability of complexes, a demonstration of subtle structural effects that strongly modify the photophysical properties, new options to get blue-greenish emitters for optoelectronic devices, and a set of ligand modifications allowing the optimization of electrochemical and excited-state properties to obtain new promising Ir(III) complexes for photoredox catalysis. These results constitute a step forward in the preparation of custom iridium-based materials crafted by excited-state engineering, which is achieved through the concerted effort of computational and synthetic chemistry along with electrochemistry and photochemistr
1,10-Phenanthrolines: Versatile building blocks for luminescent molecules, materials and metal complexes
No full text1,10-Phenanthroline entails several appealing structural and chemical properties: rigidity, planarity, aromaticity, basicity, chelating capability. This makes it a versatile starting material for synthetic organic, inorganic and supramolecular chemistry. In this tutorial review we examine how the chemical versatility of pristine 1,10-phenanthroline, a weakly fluorescent molecule, has been exploited to design many UV-Vis-NIR luminescent organic derivatives and coordination compounds with transition-metal (Ru(ii), Os(ii), Rh(iii), Cr(iii), Pt(ii), Zn(ii), Cu(i), Ag(i)) and rare-earth (Eu(iii), Tb(iii), Yb(iii), Nd(iii), Er(iii)) cations. They are utilized for many analytical and technological applications. © 2009 The Royal Society of Chemistry
Near-infrared phosphorescence in a ruthenium(ii) complex equipped with a pyridyl-1,2-azaborine ligand
Full text linkThe 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene molecule Hazab-py has been successfully used, for the first time, as a ligand in a ruthenium(ii) polypyridine complex A (with the formula [Ru(dtbbpy)2(azab-py)]+, where dtbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine). This compound was characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and its electrochemical and photophysical properties were fully investigated and compared to those of its homoleptic analogue [Ru(dtbbpy)3]2+ (B), an archetypical mono-cationic cyclometalated complex C (with the formula [Ru(dtbbpy)2(ppy)]+, where Hppy = 2-phenylpyridine), and the more structurally similar analogue [Ru(dtbbpy)2(naft-py)]+ (D), where the B-N unit of the azaborine ligand is replaced by a standard C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 C one, resulting in the 2-(naphthalen-2-yl)pyridine ligand (Hnaft-py). The presence of the novel 1,2-azaborine ligand induces a 0.51 V decrease in the redox gap of complex A, compared to that of B, leading to electrochemical and photophysical properties that resemble those of C and D. Accordingly, the azaborine complex displays an emission band extending up to the near infrared region of the spectrum (with the maximum at 765 nm in room-temperature acetonitrile solution), arising from a triplet metal-to-ligand charge-transfer (3MLCT) state. As in the case of other mono-cationic cyclometalated ruthenium(ii) complexes, A shows modest photoluminescence quantum yields (PLQYs), but higher PLQYs when compared to those of its direct C C analogue D (e.g., PLQY = 0.6 vs. 0.1% in a PMMA matrix at 298 K). Density functional theory (DFT) calculations were used to provide complete rationalization of the electronic properties of all the complexes and to identify lower-lying metal-centred triplets (3MC), responsible for the low PLQYs of such an azaborine-based ruthenium(ii) complex
Wet adsorption of a luminescent Eu-III complex on carbon nanotubes sidewalls
No full textA EuIII complex, tris-dibenzoylmethane mono-1,10-phenanthroline-europium(III) [Eu(DBM)3(Phen)], can be easily adsorbed
in situ via hydrophobic interactions to single-walled carbon nanotube (SWNT) surfaces from a methanol solution. The EuIIIcontaining
material has been comprehensively characterized via thermogravimetric analysis (TGA), UV-vis-NIR absorption
and luminescence spectroscopy, Raman spectroscopy, atomic force microscopy (AFM), high-resolution transmission electron
microscopy (HR-TEM)), Z-contrast scanning transmission electron microscopy (STEM) imaging, and energy dispersive X-ray
spectroscopy (EDS). The photophysical investigations revealed that the presence of a SWNT framework does not affect the lanthanide-
centered luminescence stemming from the characteristic electronic transitions within the 4f shell of the EuIII ions. Such straightforward
synthetic route leads to the preparation of luminescent SWNTs without significantly affecting the electronic and structural
properties of the carbon framework, opening new possibilities of designing new classes of CNTs for biomedical applications
Photochemistry and photophysics of coordination compounds: Copper
No full textCu(I) complexes and clusters are the largest class of compounds of relevant photochemical and photophysical interest based on a relatively abundant metal element. Interestingly, Nature has given an essential role to copper compounds in some biological systems, relying on their kinetic lability and versatile coordination environment. Some basic properties of Cu(I) and Cu(II) such as their coordination geometries and electronic levels are compared, pointing out the limited significance of Cu(II) compounds (d 9 configuration) in terms of photophysical properties. Well-established synthetic protocols are available to build up a variety of molecular and supramolecular architectures (e.g. catenanes, rotaxanes, knots, helices, dendrimers, cages, grids, racks, etc.) containing Cu(I)-based centers and exhibiting photo- and electroluminescence as well as light-induced intercomponent processes. By far the largest class of copper complexes investigated to date is that of Cu(I)-bisphenanthrolines ([Cu(NN)2]+) and recent progress in the rationalization of their metal-to-ligand charge-transfer (MLCT) absorption and luminescence properties are critically reviewed, pointing out the criteria by which it is now possible to successfully design highly emissive [Cu(NN)2]+ compounds, a rather elusive goal for a long time. To this end the development of spectroscopic techniques such as light-initiated time-resolved X-ray absorption spectroscopy (LITR-XAS) and femtosecond transient absorption have been rather fruitful since they have allowed us to firmly ground the indirect proofs of the molecular rearrangements following light absorption that had accumulated in the past 20 years. A substantial breakthrough towards highly emissive Cu(I) coordination compounds is constituted by heteroleptic Cu(I) complexes containing both N- and P-coordinating ligands ([Cu(NN)(PP)]+) which may exhibit luminescence quantum yields close to 30% in deaerated CH2Cl2 solution and have been successfully employed as active materials in OLED and LEC optoelectronic devices. Also copper clusters may exhibit luminescence bands of halide-to-metal charge transfer (XMCT) and/or cluster centered (CC) character and they are briefly reviewed along with miscellaneous Cu(I) compounds that recently appeared in the literature, which show luminescence bands ranging from the blue to the red spectral region. © 2007 Springer-Verlag Berlin Heidelberg
Carbazole-Terpyridine Donor-Acceptor Dyads with Rigid π-Conjugated Bridges
No full textA series of molecules in which 9H‐carbazole (electron donor, D) and 2,2′:6′,2′′‐terpyridine (electron acceptor, A) are connected through rigid π‐conjugated bridges (D‐π‐A systems) have been synthesized and their photophysical properties examined in detail, with the support of DFT calculations. The bridges are made of different sequences of ethynylene, phenylene, and anthracene groups. The synthetic strategies involve condensation of 2‐acetylpyridine with the aromatic aldehyde moiety on different functionalized π‐conjugated bridges and couplings with carbazole derivatives. The system incorporating anthracene in the bridge shows the typical absorption and emission fingerprints of this polycyclic hydrocarbon. The other systems have HOMOs and LUMOs centred, respectively, over the carbazole and the bridge and exhibit solvatochromic charge‐transfer (CT) luminescence with high photoluminescence yield up to 70 %, except when an ethynylene unit is directly attached to the carbazole ring, due to a trans‐bent non‐emissive π–σ* excited state
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
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