40000-20-2Relevant articles and documents
Efficient Access to 5-Bromo- and 5,6-Dibromophenanthroline Ligands
Stumper, Anne,Pilz, Thomas David,Schaub, Markus,G?rls, Helmar,Sorsche, Dieter,Peuntinger, Katrin,Guldi, Dirk,Rau, Sven
, p. 3799 - 3810 (2017)
Bromo-functionalized precursor molecules are essential for generating desired target compounds through cross-coupling reactions. Herein we show an improved synthetic route, feasible at low temperatures and affording high yields, to the ligands 5-bromo-1,10-phenanthroline (1) and 5,6-dibromo-1,10-phenanthroline (2). The corresponding ruthenium complexes, containing various equivalents of ligand 2, are easily accessible in high yields, including the analogue of tris-homoleptic [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine), [Ru(2)3]2+. X-ray diffraction analyses have provided detailed information on the structures of the ligands and their corresponding metal complexes. An investigation of the electrochemical properties has provided detailed information on the 3MLCT state localized on 2. We show the conversion of heteroleptic ruthenium complexes of these ligands in Suzuki cross-coupling reactions whereas the ligands did not undergo reaction under the same conditions.
Synthesis, Characterization and Photobiological Studies of Ru(II) Dyads Derived from α-Oligothiophene Derivatives of 1,10-Phenanthroline
Monro, Susan,Cameron, Colin G.,Zhu, Xiaolin,Colón, Katsuya L.,Yin, Huimin,Sainuddin, Tariq,Hetu, Marc,Pinto, Mitch,Fuller, Anderson,Bennett, Leah,Roque, John,Sun, Wenfang,McFarland, Sherri A.
, p. 267 - 279 (2019)
Three new bis(2,2′-bipyridine)-heteroleptic Ru(II) dyads incorporating thienyl groups (n?=?1–3, compounds 1, 2 and 3, respectively) appended to 1,10-phenanthroline were synthesized and characterized to investigate the impact of n on the photophysical and photobiological properties within the series. All three complexes showed unstructured emission near 618?nm from a triplet metal-to-ligand charge transfer (3MLCT) state with a lifetime (τem) of approximately 1?μs. Transient absorption measurements revealed an additional excited state that was nonemissive and long-lived (τTA?=?43?μs for 2 and 27?μs for 3), assigned as a triplet intraligand (3IL) state that was accessible only in 2 and 3. All three complexes were strong singlet oxygen (1O2) sensitizers, with quantum yields (Φ?) for 2 and 3 being the largest (74–78%), and all three were photocytotoxic to cancer cells with visible light activation in the order: 3?>?2?>?1. Cell-free DNA photodamage followed the same trend, where potency increased with decreasing 3IL energy. Compounds 2 and 3 also showed in?vitro photobiological effects with red light (625?nm), where their molar absorptivities were ?1?cm?1. These findings highlight that Ru(II) dyads derived from α-oligothiophenes directly appended to 1,10-phenanthroline—namely 2 and 3—possess low-lying 3IL states that are highly photosensitizing, and they may therefore be of interest for photobiological applications such as photodynamic therapy (PDT).
Synthesis of metallo-supramolecular polymers using 5,5′-linked bis(1,10-phenanthroline) ligands
Hossain, Md. Delwar,Higuchi, Masayoshi
, p. 753 - 758 (2013)
5,5′-Linked bis(1,10-phenanthroline)s were synthesized as new bidentate ligands by a palladium-catalyzed Suzuki-type cross-coupling reaction. Coordination of the ligands to Cu(II), Ni(II), Ag(I), and Zn(II) ions resulted in metallo-supramolecular polymer formation. The 1:1 complexation of the ligands and the metal ions was confirmed by UV-vis titration experiments. The high molecular weights of more than 105 Da, caused by the high complexation constants, were confirmed by the SEC-Viscometry-RALLS method. Georg Thieme Verlag Stuttgart New York.
Palladium Nanoparticles Encapsulated in [M(C19H11N2O2)2·H2O] (M = Co and Mn) as a Potential Catalyst for the Homocoupling of Aryl Halides
Jana, Ajay Kumar,Hota, Raghunandan,Natarajan, Srinivasan
, p. 6992 - 6999 (2016)
A new ligand, 4-(1,10-phenanthrolin-6-yl)benzoic acid, has been synthesized and employed to prepare new inorganic coordination polymer compounds, [M(C19H11N2O2)2·H2O] (M = Co, Mn). Both the compounds have identical structures formed by the connectivity between octahedral metal centers and the ligand, giving rise to a two-dimensional structure. The 2D structure is interpenetrated by identical units and forms a 2-fold interpenetrated structure. The lattice water molecules can be reversibly removed without altering the gross framework structure. The water removal has been investigated using in situ IR, PXRD, and in situ single-crystal XRD studies. Pd nanoparticles, prepared employing known procedures, were incorporated within the compound. We have successfully encapsulated up to 6.8% of Pd with a particle size of 4.8 ± 0.3 nm in the compound. The Pd@MOF compound was examined for homocoupling of aryl halides, resulting in good yields and recyclability. Magnetic studies indicate antiferromagnetic behavior in both the compounds with good orbital contribution for the cobalt compound.
Chemistry on the Complex: Derivatization of TiO4N2-Based Complexes and Application to Multi-Step Synthesis
Chaumont, Alain,Kyritsakas, Nathalie,Mobian, Pierre,Scarpi-Luttenauer, Matthieu
, p. 17910 - 17920 (2021/12/09)
The chemistry on octahedral TiO4N2-complexes is described. The Ti(IV)-based precursors are composed of two 3,3’-diphenyl-2,2’-biphenolato ligands (1) and one substituted 1,10-phenanthroline ligand (2-5). The application of imine condensation, palladium-catalyzed C?C bond formation or copper-catalysed azide-alkyne cycloaddition allowed the grafting of various new groups onto these species. In particular Sonogashira reactions permitted to observe an excellent conversion of the starting complexes. This systematic study enabled to compile the factors required to preserve the framework of the complexes in the course of a chemical transformation. Thanks to this chemistry realized on the complex, the Ti(1)2 fragment was used as a protecting group to develop a multi-step synthesis of a bis-phenanthroline compound (12), for which the synthesis without this protection failed. Thus, a dinuclear complex [Ti2(1)4(12)] was first prepared starting from complex precursor bearing an acetylenic function via a Hay coupling reaction. This was followed by a deprotection step affording 12. Overall, this work illustrates how the Ti(1)2 fragment could be an useful tool for the preparation of unprecedented diimine compounds.
A O-phenanthrene derivatives and their organic electroluminescent device (by machine translation)
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Paragraph 0058; 0060-0062, (2018/10/19)
The present invention provides a O-phenanthrene derivatives and their organic electroluminescent device, relates to organic photoelectric material technical field. The compound preparation method is simple, easily available raw materials, has good thermal stability and chemical stability, while at the same time has very good film-forming property and the cavity transmitting capacity. Such compound has suitable maximum has been molecular orbit level, high T1 value and a high refractive index, as applied to the light-emitting layer in the OLED device, can realize the light-emitting layer of the charge equalization, can markedly improve the luminous efficiency of the device, the service life of the heat resistance and, at the same time also can effectively reduce the driving voltage of the device, is a kind of excellent performance of the OLED material. (by machine translation)