Racemic Compound FormationversusConglomerate Formation with [M(bpy)3](PF6)2 (M = Ni, Zn, Ru); Molecular and Crystal Structures

Breu, Josef; Domel, Holger; Stoll, Alexander

doi:10.1002/1099-0682(200011)2000:11<2401::aid-ejic2401>3.0.co;2-3

Cited by 52 publications

(21 citation statements)

References 40 publications

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“…On the other hand, q36k represents a higher quality structure and will be discussed here. As expected, the average chelate angle (N-Ru-N) and corresponding average Ru-N distance for complex 5 (data from q36k) are larger than in the case of the famous [Ru(bpy) 3 ] 2+ (82.9(3) • vs. 78.9(2) • ; 2.117(13) Å vs. 2.063(6) Å) [38][39][40]. Gratifyingly, these values align with structural data previously available for [Ru(daf) 3 ] 2+ , confirming that use of daf or Me 2 daf to form homoleptic Ru(II) complexes results in wider chelate angles and longer Ru-N distances in both cases [41].…”

Section: Electronic Absorption Ir and X-ray Diffraction Studiessupporting

confidence: 87%

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

et al. 2020

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4,5-diazafluorene (daf) and 9,9’-dimethyl-4,5-diazafluorene (Me2daf) are structurally similar to the important ligand 2,2’-bipyridine (bpy), but significantly less is known about the redox and spectroscopic properties of metal complexes containing Me2daf as a ligand than those containing bpy. New complexes Mn(CO)3Br(daf) (2), Mn(CO)3Br(Me2daf) (3), and [Ru(Me2daf)3](PF6)2 (5) have been prepared and fully characterized to understand the influence of the Me2daf framework on their chemical and electrochemical properties. Structural data for 2, 3, and 5 from single-crystal X-ray diffraction analysis reveal a distinctive widening of the daf and Me2daf chelate angles in comparison to the analogous Mn(CO)3(bpy)Br (1) and [Ru(bpy)3]2+ (4) complexes. Electronic absorption data for these complexes confirm the electronic similarity of daf, Me2daf, and bpy, as spectra are dominated in each case by metal-to-ligand charge transfer bands in the visible region. However, the electrochemical properties of 2, 3, and 5 reveal that the redox-active Me2daf framework in 3 and 5 undergoes reduction at a slightly more negative potential than that of bpy in 1 and 4. Taken together, the results indicate that Me2daf could be useful for preparation of a variety of new redox-active compounds, as it retains the useful redox-active nature of bpy but lacks the acidic, benzylic C–H bonds that can induce secondary reactivity in complexes bearing daf.

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Section: Electronic Absorption Ir and X-ray Diffraction Studiessupporting

confidence: 87%

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

et al. 2020

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“…For the three ruthenium complexes ( 1 – 3 ), students were provided with a set of experimental data retrieved from the literature, including X-ray structures, − absorption and emission spectra, emission quantum yield and lifetimes, and photostability data. − , …”

Section: The Problem To Tacklementioning

confidence: 99%

Teaching Inorganic Photophysics and Photochemistry with Three Ruthenium(II) Polypyridyl Complexes: A Computer-Based Exercise

et al. 2015

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Among computational methods, DFT (density functional theory) and TD-DFT (time-dependent DFT) are widely used in research to describe, inter alia, the optical properties of transition metal complexes. Inorganic/physical chemistry courses for undergraduate students treat such methods, but quite often only from the theoretical point of view. In the calculation exercise herein described, students are guided step by step through the computational study of the photophysics and photochemistry of polypyridyl Ru(II) d6-metal complexes. In particular, by means of DFT and TD-DFT calculations, they are asked to examine and interpret a set of experimental data describing the absorption, emission, and photochemical behavior of three structurally related ruthenium complexes, namely, [Ru(bpy)3]2+ (1), [Ru(tpy)2]2+ (2), and [Ru(bpy)2(py)2]2+ (3). These complexes are particularly suitable for an educational purpose since they exhibit distinct optical and photochemical properties despite being structurally akin to each other. In the computational chemistry laboratory, the instructor progressively guides students through the preparation of DFT and TD-DFT inputs and the use of software for the analysis of output files, including visualization of optimized geometries, absorption spectra, orbitals, and spin density surfaces. The exercise covers training of students in several key concepts concerning the photophysics and photochemistry of transition metal complexes. These include Franck-Condon transitions and the role of 3MLCT (metal-to-ligand charge transfer) and 3MC (metal-centered or ligand-field) states in luminescence and ligand photodissociation processes. Notably, the mixed character of this exercise allows its integration with theoretical and experimental activities and the design of truly multidisciplinary courses

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“…[ 3 ] Nevertheless, these strategies still suffer from defects including complex manipulation, low photoconversion efficiency, and high background ECL signal. More importantly, the notorious aggregation‐caused quenching (ACQ) resulted from strong π‐π interactions between adjacent Ru‐bpy molecules is often overlooked upon aggregation or crystallization, [ 4 ] greatly impairing its ECL efficiency to a certain extent, thus restricting further applications in all‐solid‐state ECL sensing and imaging as well as light‐emitting devices.…”

Section: Introductionmentioning

confidence: 99%

Crystallization‐Induced Enhanced Electrochemiluminescence from a New Tris(bipyridine)ruthenium(II) Derivative

Han

Cao

Wang

et al. 2023

Adv Funct Materials

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Classic tris(bipyridine)ruthenium(II) complex (Ru‐bpy) with high electrochemiluminescence (ECL) efficiency still suffers from a serious aggregation‐caused quenching (ACQ) problem, which greatly weakens its ECL efficiency to restrict further applications in solid‐state ECL imaging and light‐emitting devices. Herein, the crystallization‐induced enhanced ECL (CIE‐ECL) of tris(bipyridine)ruthenium(II) derivatives (Ru‐TPE) are reported by decorating Ru‐bpy with inherent aggregation‐induced emission active tetraphenylethene (TPE), which effectively eliminates the detrimental π–π stacking interactions and thus helps Ru‐bpy surmount notorious ACQ effect in the aqueous phase. The Ru‐TPE shows negligible ECL emission in solution but produces a strong ECL emission upon crystallization. Surprisingly, the ECL efficiency of Ru‐TPE crystals is 20 and 3 times higher than that of its solution and Ru‐bpy crystals, respectively. Experimental and structural analysis reveals that such a CIE‐ECL effect originates from the restricted intramolecular rotation and ordered molecular packing. Moreover, the high‐resolution ECL imaging of a single Ru‐TPE crystal is successfully demonstrated. This work provides a new design strategy for achieving high efficiency in solid‐state ECL imaging and devices.

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Racemic Compound FormationversusConglomerate Formation with [M(bpy)3](PF6)2 (M = Ni, Zn, Ru); Molecular and Crystal Structures

Cited by 52 publications

References 40 publications

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

Teaching Inorganic Photophysics and Photochemistry with Three Ruthenium(II) Polypyridyl Complexes: A Computer-Based Exercise

Crystallization‐Induced Enhanced Electrochemiluminescence from a New Tris(bipyridine)ruthenium(II) Derivative

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