Enhanced luminescence oxygen sensing property of Ru(II) bispyridine complexes by ligand modification

Wu, Wanhua; Ji, Shaomin; Wu, Wenting; Guo, Huimin; Wang, Xin; Zhao, Jianzhang; Wang, Zhonggang

doi:10.1016/j.snb.2010.06.043

Cited by 26 publications

(19 citation statements)

References 39 publications

(58 reference statements)

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“…[28] After excitation, a triplet state could be reached from an excited singlet state by intersystem crossing having a rate coefficient close to unity. Thus, fluorescence from the excited singlet to the ground state is rarely observed and emissions are mainly phosphorescent and have relatively long lifetimes.…”

Section: Resultsmentioning

confidence: 99%

Polydimethylsiloxane core–polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors

Xue

Behera

et al. 2014

Sensors and Actuators B: Chemical

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Real-time, continuous monitoring of local oxygen contents at the cellular level is desirable both for the study of cancer cell biology and in tissue engineering. In this paper, we report the successful fabrication of polydimethylsiloxane (PDMS) nanofibers containing oxygen-sensitive probes by electrospinning and the applications of these fibers as optical oxygen sensors for both gaseous and dissolved oxygen. A protective ‘shell’ layer of polycaprolactone (PCL) not only maintains the fiber morphology of PDMS during the slow curing process but also provides more biocompatible surfaces. Once this strategy was perfected, tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) (Ru(dpp)) and platinum octaethylporphyrin (PtOEP) were dissolved in the PDMS core and the resulting sensing performance established. These new core-shell sensors containing different sensitivity probes showed slight variations in oxygen response but all exhibited excellent Stern-Volmer linearity. Due in part to the porous nature of the fibers and the excellent oxygen permeability of PDMS, the new sensors show faster response (<0.5 s) −4–10 times faster than previous reports – than conventional 2D film-based oxygen sensors. Such core-shell fibers are readily integrated into standard cell culture plates or bioreactors. The photostability of these nanofiber-based sensors was also assessed. Culture of glioma cell lines (CNS1, U251) and glioma-derived primary cells (GBM34) revealed negligible differences in biological behavior suggesting that the presence of the porphyrin dyes within the core carries with it no strong cytotoxic effects. The unique combination of demonstrated biocompatibility due to the PCL ‘shell’ and the excellent oxygen transparency of the PDMS core makes this particular sensing platform promising for sensing in the context of biological environments.

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Section: Resultsmentioning

confidence: 99%

Polydimethylsiloxane core–polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors

Xue

Behera

et al. 2014

Sensors and Actuators B: Chemical

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“…In attempts to leverage the abundant and freely available solar energy, new developments in the design and application of these classical TMPRCs have come to light, for example, the so-called cooperative catalysis, where a photoredox catalytic system is used in synergy with another TM catalyst to facilitate chemical transformations [5][6][7]. Other widespread applications of the parent TMPRC platforms and other closely related iridium and ruthenium derivatives include photovoltaic-like dye-sensitized solar cells (DSSCs) [8,9], chemical sensing [10,11], photodynamic therapy [12,13], etc. The basic photophysics of classical TMPRCs is well established and summarized in Figure 1a for the archetypal [Ru(bpy)3] 2+ (bpy = bipyridine) system [3,15,17,18].…”

Section: Introductionmentioning

confidence: 99%

“…Note that the ∆ρ(r) map of the latter process is given for the reduction direction (S0 D red ) for the sake of consistency.Probably the most spectacular insight revealed by this analysis is the disclosure of the localization of the transferred charge to bipyridine and terpyridine ligand(s) in heteroleptic carbene complexes. Namely, going from [Ru(bpy)3] 2+ to [Ru(bpy)2(py-fNHC Me )] 2+(10) and [Ru(tpy)(C^N^C)] 2+(12), the charge transferred from the metal to the ligand which was delocalized uniformly amongst the three bpy ligands in [Ru(bpy)3] 2+ , becoming localized to the two bpy ligands in [Ru(bpy)2(py-fNHC Me )] 2+ and to the tpy ligand in [Ru(tpy)(C^N^C)] 2+…”

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confidence: 99%

A DFT Study on the Redox Active Behavior of Carbene and Pyridine Ligands in the Oxidative and Reductive Quenching Cycles of Ruthenium Photoredox Catalysts

Medina

Pintér

2020

Catalysts

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In this study, a detailed look at the electronic structure changes induced by photon absorption and of the succeeding redox events of the oxidative and reductive quenching cycles of ruthenium–carbene and ruthenium–pyridine photoredox catalysts is provided through an arsenal of density functional theory-based techniques including electron density difference Δρ(r) maps, spin-density distributions, and the non-covalent interaction analysis. We introduced an efficient computational protocol to obtain accurate equilibrium structures and ground-state reduction potentials for these types of complexes, substantiated via a direct comparison to empirical X-ray structures and cyclic voltammetry measurements, respectively. Moreover, we demonstrated the utility of a hitherto unexplored approach to compute excited-state redox potentials based on the Gibbs free energy of the triplet metal-to-ligand charge transfer state (3MLCT). The analyzed Δρ(r) maps revealed the characteristic features of, for example, metal- and ligand-centered reductions and oxidations in both ground and excited states and MLCT processes, disclosing the active participation of carbene ligands in the redox events of homoleptic systems. Beyond analyzing ligand–ligand non-covalent interactions and redox-active behaviors of carbene and pyridine ligands side by side, the effect of such groups on the kinetics of 3MLCT to 3MC transition was scrutinized.

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“…[7, 18a, 33] Moreover, the lifetimes of the T 1 excited states of the normal Ir III complexes are short (usually less than 5.0 ms). [1, 8-12, 15, 18b, 19, 34, 35] We proposed that these photophysical processes could be enhanced by the longlived T 1 excited states, as has been demonstrated in luminescent oxygen sensing [36][37][38][39][40][41][42][43][44][45] and in triplet-triplet annihilation (TTA) upconversion. [43][44][45][46][47][48][49][50][51][52][53] Thus, the preparation of cyclometalated Ir III complexes with intense visible-light absorption and long-lived T 1 excited states is of great interest.…”

Section: Introductionmentioning

confidence: 99%

Long‐Lived Room‐Temperature Deep‐Red‐Emissive Intraligand Triplet Excited State of Naphthalimide in Cyclometalated Ir^III Complexes and its Application in Triplet‐Triplet Annihilation‐Based Upconversion

Sun

Zhao

2012

Chemistry A European J

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Cyclometalated Ir(III) complexes with acetylide ppy and bpy ligands were prepared (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine) in which naphthal (Ir-2) and naphthalimide (NI) were attached onto the ppy (Ir-3) and bpy ligands (Ir-4) through acetylide bonds. [Ir(ppy)(3)] (Ir-1) was also prepared as a model complex. Room-temperature phosphorescence was observed for the complexes; both neutral and cationic complexes Ir-3 and Ir-4 showed strong absorption in the visible range (ε=39,600 M(-1) cm(-1) at 402 nm and ε=25,100 M(-1) cm(-1) at 404 nm, respectively), long-lived triplet excited states (τ(T)=9.30 μs and 16.45 μs) and room-temperature red emission (λ(em)=640 nm, Φ(p)=1.4 % and λ(em)=627 nm, Φ(p)=0.3 %; cf. Ir-1: ε=16,600 M(-1) cm(-1) at 382 nm, τ(em)=1.16 μs, Φ(p)=72.6 %). Ir-3 was strongly phosphorescent in non-polar solvent (i.e., toluene), but the emission was completely quenched in polar solvents (MeCN). Ir-4 gave an opposite response to the solvent polarity, that is, stronger phosphorescence in polar solvents than in non-polar solvents. Emission of Ir-1 and Ir-2 was not solvent-polarity-dependent. The T(1) excited states of Ir-2, Ir-3, and Ir-4 were identified as mainly intraligand triplet excited states ((3)IL) by their small thermally induced Stokes shifts (ΔE(s)), nanosecond time-resolved transient difference absorption spectroscopy, and spin-density analysis. The complexes were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion and quantum yields of 7.1 % and 14.4 % were observed for Ir-2 and Ir-3, respectively, whereas the upconversion was negligible for Ir-1 and Ir-4. These results will be useful for designing visible-light-harvesting transition-metal complexes and for their applications as triplet photosensitizers for photocatalysis, photovoltaics, TTA upconversion, etc.

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Enhanced luminescence oxygen sensing property of Ru(II) bispyridine complexes by ligand modification

Cited by 26 publications

References 39 publications

Polydimethylsiloxane core–polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors

Polydimethylsiloxane core–polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors

A DFT Study on the Redox Active Behavior of Carbene and Pyridine Ligands in the Oxidative and Reductive Quenching Cycles of Ruthenium Photoredox Catalysts

Long‐Lived Room‐Temperature Deep‐Red‐Emissive Intraligand Triplet Excited State of Naphthalimide in Cyclometalated Ir^III Complexes and its Application in Triplet‐Triplet Annihilation‐Based Upconversion

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Enhanced luminescence oxygen sensing property of Ru(II) bispyridine complexes by ligand modification

Cited by 26 publications

References 39 publications

Polydimethylsiloxane core–polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors

Polydimethylsiloxane core–polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors

A DFT Study on the Redox Active Behavior of Carbene and Pyridine Ligands in the Oxidative and Reductive Quenching Cycles of Ruthenium Photoredox Catalysts

Long‐Lived Room‐Temperature Deep‐Red‐Emissive Intraligand Triplet Excited State of Naphthalimide in Cyclometalated IrIII Complexes and its Application in Triplet‐Triplet Annihilation‐Based Upconversion

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Long‐Lived Room‐Temperature Deep‐Red‐Emissive Intraligand Triplet Excited State of Naphthalimide in Cyclometalated Ir^III Complexes and its Application in Triplet‐Triplet Annihilation‐Based Upconversion