Synthesis, structure and photophysical properties of cationic Ir(III) complexes with functionalized 1,10-phenanthroline ancillary ligands

Shan, Guo‐Gang; Li, Haibin; Cao, Hong‐Tao; Zhu, Dongxia; Su, Zhong‐Min; Liao, Yi

doi:10.1016/j.jorganchem.2012.04.018

Cited by 16 publications

(6 citation statements)

References 40 publications

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“…Cyclometallated iridium(III) complexes have found applications in electroluminescent instruments such as sensors and light-emitting devices and in photocatalysis because of their high emission efficiencies, photo/thermal stabilities and easy tunability of the emission wavelength (Zhao et al, 2010;Shan et al, 2012). In this regard, a variety of cyclometallated iridium complexes have been reported and most of them have potential for the aforementioned applications (Flamigni et al, 2008;Li et al, 2011).…”

Section: Chemical Contextmentioning

confidence: 99%

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Synthesis and crystal structure of (1,10-phenanthroline-κ² N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ² N ²,C ¹]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

2020

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The cationic complex in the title compound, [Ir(C9H7N2)2(C12H8N2)]PF6, comprises two phenylpyrazole (ppz) cyclometallating ligands and one 1,10-phenanthroline (phen) ancillary ligand. The asymmetric unit consists of one [Ir(ppz)2(phen)]+ cation and one [PF6]− counter-ion. The central IrIII ion is six-coordinated by two N atoms and two C atoms from the two ppz ligands as well as by two N atoms from the phen ligand within a distorted octahedral C2N4 coordination set. In the crystal structure, the [Ir(ppz)2(phen)]+ cations and PF6 − counter-ions are connected with each other through weak intermolecular C—H...F hydrogen bonds. Additional C—H...π interactions between the rings of neighbouring cations consolidate the three-dimensional network. Electron density associated with additional disordered solvent molecules inside cavities of the structure was removed with the SQUEEZE procedure in PLATON [Spek (2015). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not take into account the unknown solvent molecule(s). The title compound has a different space-group symmetry (C2/c) from its solvatomorph (P21/c) comprising 1.5CH2Cl2 solvent molecules per ion pair.

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Section: Chemical Contextmentioning

confidence: 99%

“…The three other structures comprise derivatives of the phen ligand, viz. JUPTEV/ JUPTAR (Howarth et al, 2015) and DUCWOZ (Shan et al, 2012).…”

Section: Database Surveymentioning

confidence: 99%

Synthesis and crystal structure of (1,10-phenanthroline-κ² N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ² N ²,C ¹]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

2020

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“…25,32,33,40 The emission maxima ranged from 600 to 635 nm, as shown in Figure S18, and are bathochromically shifted for Re-pyr, Re-ind, and Re-cbz in comparison to Re-phen as a result of a more efficient stabilization of the 3 MLCT Re→NN excited state by the presence of additional aromatic rings. 28,41,42 The PL quantum yields (Φ PL ) and lifetimes (τ PL ) increased in the order Re-cbz < Reind < Re-pyr < Re-phen, as shown in Table 2, following the decrease in the number of aromatic rings of the substituent in the NN ligand. The presence of the N-heterocyclic substituents favored the nonradiative decay that competes with the radiative deactivation of the excited state.…”

Section: Spectroscopic Electrochemical and Photophysicalmentioning

confidence: 95%

“…The molecular engineering of new polypyridyl ligand scaffolds is a convenient strategy to red-shift the light absorption by the compounds while also modulating their properties to achieve high catalytic performances. The attachment of N-heterocyclic moieties to the polypyridyl ligand, for example, has been shown to increase considerably the visible-light absorption range and molar absorptivity of the complexes in comparison to the unsubstituted counterparts, and also modulates the electronic properties and reactivity of the compounds. ,− Recent investigations on the functionalization of the bypyridyl moiety of Lehn catalysts with π-conjugated electron donor pyrene groups, or N -phenylcarbazole and BF 2 -chelated dipyrromethene, exhibited impressive photocatalytic activity and stability. Motivated by these systems, in this work a series of fac -[Re(NN)(CO) 3 Cl] complexes, in which NN is a 1,10-phenanthroline ligand having at its 4,7 positions the N-heterocyclic substituents pyrrole, indole, or carbazole, as shown in Figure , were investigated as single-molecule photocatalysts for promoting visible-light-driven reduction of CO 2 .…”

Section: Introductionmentioning

confidence: 99%

Visible-Light-Driven Photocatalytic CO₂ Reduction by Re(I) Photocatalysts with N-Heterocyclic Substituents

et al. 2022

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The properties and reactivity of metal complex photocatalysts for solar-to-fuel conversion can be conveniently controlled by the molecular design of their ligands. In this work, rhenium(I) tricarbonyl polypyridyl compounds, fac-[Re(NN)(CO) 3 Cl], where NN is a 1,10-phenanthroline ligand having pyrrole (Re-pyr), indole (Re-ind), or carbazole (Re-cbz) groups attached to its 4 and 7 positions, were investigated as photocatalysts for reducing CO 2 to CO. These complexes can harvest light in the visible region and displayed an exceptionally high photocatalytic performance, with an up to 10-fold increase in the TON CO values compared to the unsubstituted Re-phen parental complex. Re-pyr was the best performing photocatalyst in this series, with a TON CO of 125 after 24 h and Φ CO = 0.22. The TON CO of Re-pyr, Re-ind, and Re-cbz surpassed even the most efficient Lehn-type photocatalysts reported to date to promote the photoreduction of CO 2 using triethanolamine as the sacrificial electron donor, without a second molecule working as a light absorber. The excellent photocatalytic performance of this series was intimately related to the presence of N-heterocyclic substituents, which enhanced the visible-light absorption properties of the compounds, favored the kinetics and thermodynamics of each individual step of the photocatalysis, inhibited deactivation of the photocatalysts by dimerization, stabilized reduced intermediates, and unlocked an alternative CO 2 photoreduction pathway that proceeds predominantly through a two-electron reduced species [Re(NN)(CO) 3 ] − .

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“…Syntheses 4,7-Di(9H-carbazol-9-yl)-1,10-phenanthroline (cbz 2 phen). The synthesis was performed as described previously 67,73,74 with modifications. 1.34 g (8.00 mmol) of carbazole and 0.95 g (8.5 mmol) of potassium tert-butoxide were added to dry THF (40 mL) under an argon atmosphere and heated to reflux.…”

Section: Methodsmentioning

confidence: 99%

Contrasting photophysical properties of rhenium(i) tricarbonyl complexes having carbazole groups attached to the polypyridine ligand

et al. 2016

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In the present work, new rhenium(i) polypyridyl compounds, fac-[Re(L)(CO)3(cbz2phen)](+/0) where cbz2phen = 4,7-di(9H-carbazol-9-yl)-1,10-phenanthroline and L = Cl(-), pyridine (py) or 2-aminomethylpyridine (ampy) were synthesized and characterized by (1)H NMR, UV-Vis and IR spectroscopy combined with theoretical calculations using time-dependent density functional theory (TD-DFT). Their photophysical properties were investigated by steady state and time-resolved emission spectroscopy. These compounds show a strong and broad absorption band around 350-500 nm that, also by TD-DFT, corresponds to the carbazol → phenanthroline intraligand charge transfer transition, (1)ILCTcbz2phen, with some contribution of the Re(i) → phenanthroline metal-to-ligand charge transfer transition, (1)MLCTRe→cbz2phen. In contrast to typical Re(i) polypyridyl complexes, cbz2phen-based Re(i) compounds exhibit two emission maxima in CH3CN solution and relatively low emission quantum yields, 10(-3)-10(-2). Solution phase time-resolved photoluminescence and excited state quenching experiments provided meaningful information on the presence of multiple emitter states after light excitation, which were identified as an (1)ILCTcbz2phen excited state deactivation at higher energies and a long-lived phosphorescence attributed to the (3)MLCTRe→cbz2phen excited state. When embedded into a PMMA matrix, the radiative decay from the singlet state is inhibited and the contribution of both (3)MLCT and (3)ILCTcbz2phen to the luminescence is observed. The photophysics of these Re(i) compounds reported herein provide new insights into the understanding of substitutional groups on the polypyridyl ligands that are relevant to practical and fundamental development of photo-induced molecular devices.

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Synthesis, structure and photophysical properties of cationic Ir(III) complexes with functionalized 1,10-phenanthroline ancillary ligands

Cited by 16 publications

References 40 publications

Synthesis and crystal structure of (1,10-phenanthroline-κ² N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ² N ²,C ¹]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

Synthesis and crystal structure of (1,10-phenanthroline-κ² N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ² N ²,C ¹]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

Visible-Light-Driven Photocatalytic CO₂ Reduction by Re(I) Photocatalysts with N-Heterocyclic Substituents

Contrasting photophysical properties of rhenium(i) tricarbonyl complexes having carbazole groups attached to the polypyridine ligand

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Synthesis, structure and photophysical properties of cationic Ir(III) complexes with functionalized 1,10-phenanthroline ancillary ligands

Cited by 16 publications

References 40 publications

Synthesis and crystal structure of (1,10-phenanthroline-κ2 N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ2 N 2,C 1]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

Synthesis and crystal structure of (1,10-phenanthroline-κ2 N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ2 N 2,C 1]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

Visible-Light-Driven Photocatalytic CO2 Reduction by Re(I) Photocatalysts with N-Heterocyclic Substituents

Contrasting photophysical properties of rhenium(i) tricarbonyl complexes having carbazole groups attached to the polypyridine ligand

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Synthesis and crystal structure of (1,10-phenanthroline-κ² N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ² N ²,C ¹]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

Synthesis and crystal structure of (1,10-phenanthroline-κ² N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ² N ²,C ¹]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules

Visible-Light-Driven Photocatalytic CO₂ Reduction by Re(I) Photocatalysts with N-Heterocyclic Substituents