Zirconium(IV) Metallocavitands As Blue-Emitting Materials

Iden, Hassan; Bi, Weihong; Morin, Jean‐François; Fontaine, Frédéric‐Georges

doi:10.1021/ic402602d

Cited by 18 publications

(13 citation statements)

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“…This luminescence was quenched by molecular oxygen upon exposure to air. Noteworthy luminescent properties were reported also for a series of CpZr carboxylate metallocavitands having various appended nitrogen-containing aromatic functional groups, which exhibited a blue-light luminescence in THF solutions . A fundamental contribution to the area of early transition metal-based photoactive compounds was made by Milsmann et al in 2016, when they reported a homoleptic Zr complex with two tridentate 2,6-bis(pyrrolyl)pyridine (PDP) ligands, featuring a CT absorption band in the visible region (528 nm) and exhibiting luminescence in solution with quantum yields comparable with the archetypal [Ru(bpy) 3 ] 2+ cation .…”

Section: Introductionmentioning

confidence: 99%

Luminescent Cationic Group 4 Metallocene Complexes Stabilized by Pendant N-Donor Groups

et al. 2021

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Cationic group 4 metallocene complexes with pendant imine and pyridine donor groups were prepared as stable crystalline [B(C6F5)4]− salts either by protonation of the intramolecularly bound ketimide moiety in neutral complexes [(η5-C5Me5){η5-C5H4CMe2CMe2C(R)N-κN}MCl] (M = Ti, Zr, Hf; R = t-Bu, Ph) by PhNMe2H+[B(C6F5)4]− to give [(η5-C5Me5){η5-C5H4CMe2CMe2C(R)NH-κN}MCl]+[B(C6F5)4]− or by chloride ligand abstraction from the complexes [(η5-C5Me5)(η5-C5H4CMe2CH2C5H4N)MCl2] (M = Ti, Zr) by Li[B(C6F5)4]·2.5Et2O to give [(η5-C5Me5)(η5-C5H4CMe2CH2C5H4N-κN)MCl]+[B(C6F5)4]−. Solid state structures of the new compounds were established by X-ray diffraction analysis, and their electrochemical behavior was studied by cyclic voltammetry. The cationic complexes of Zr and Hf, compared to the corresponding neutral species, exhibited significantly enhanced luminescence predominantly from triplet ligand-to-metal (3LMCT) excited states with lifetimes up to 62 μs and quantum yields up to 58% in the solid state. DFT calculations were performed to explain the structural features and optical and electrochemical properties of the complexes.

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Section: Introductionmentioning

confidence: 99%

Luminescent Cationic Group 4 Metallocene Complexes Stabilized by Pendant N-Donor Groups

et al. 2021

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“…The ligands (L 1 and L 2 ) were synthesized following a slightly modified procedure. 76 To the suspended aqueous solution of isonicotinic acid (1 mmol, 123 mg, 5 mL water), sodium hydroxide (1 mmol, 40 mg) was added to make isonicotinic acid completely soluble in water. The pH of the solution was adjusted 6−7 by adding 2(N) dil.…”

Section: ■ Introductionmentioning

confidence: 99%

Coordination-Driven Self-assembly of Cyclopentadienyl-Capped Heterometallic Zr–Pd Cages

Maity

Howlader

Mukherjee

2018

Crystal Growth & Design

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A series of heterometallic Zr 3 Pd 3 -trigonal bipyramidal compounds (1−4) was synthesized by twocomponent coordination-driven self-assembly of cis-protected palladium(II) 90°acceptors with trinuclear carboxylatebridged zirconocene-based tripodal metallo-ligands. To avoid multiple product formation using two different metal acceptors, we chose trinuclear Zr(IV) metallo-ligands as donors. All the compounds were characterized by NMR and single crystal X-ray diffraction. Among the compounds, the water-soluble compound 2 is capable to encapsulate aromatic guests such as naphthalene and 2-naphthaldehyde. The encapsulation of the guests was confirmed by NMR and UV−vis spectrometry. The binding constants as well as corresponding Gibbs free energy changes were calculated separately from the 1 H NMR titration of compound 2 with guests (naphthalene/2naphthaldehyde).

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“…Since in this preliminary study we used AuNPs loaded with multiple ODNs, a fairly polydisperse mixture of aggregates was observed ranging from aggregates of 3–4 AuNPs to gigantic aggregates of hundred AuNPs. The controlled-assembly (controlled aggregate size and distance) of SMDH/AuNPs complexes by using AuNPs loaded with single-strand ODN and their structural characterization is currently under investigation. − …”

Section: Results and Discussionmentioning

confidence: 99%

Synthesis of Small-Molecule/DNA Hybrids through On-Bead Amide-Coupling Approach

et al. 2017

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Small molecule/DNA hybrids (SMDHs) have been considered as nanoscale building blocks for engineering 2D and 3D supramolecular DNA assembly. Herein, we report an efficient on-bead amide-coupling approach to prepare SMDHs with multiple oligodeoxynucleotide (ODN) strands. Our method is high yielding under mild and user-friendly conditions with various organic substrates and homo- or mixed-sequenced ODNs. Metal catalysts and moisture- and air-free conditions are not required. The products can be easily analyzed by LC-MS with accurate mass resolution. We also explored nanometer-sized shape-persistent macrocycles as novel multitopic organic linkers to prepare SMDHs. SMDHs bearing up to six ODNs were successfully prepared through the coupling of arylenethynylene macrocycles with ODNs, which were used to mediate the assembly of gold nanoparticles.

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Zirconium(IV) Metallocavitands As Blue-Emitting Materials

Cited by 18 publications

References 50 publications

Luminescent Cationic Group 4 Metallocene Complexes Stabilized by Pendant N-Donor Groups

Luminescent Cationic Group 4 Metallocene Complexes Stabilized by Pendant N-Donor Groups

Coordination-Driven Self-assembly of Cyclopentadienyl-Capped Heterometallic Zr–Pd Cages

Synthesis of Small-Molecule/DNA Hybrids through On-Bead Amide-Coupling Approach

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