Effect of substituents on properties of diphenylphosphoryl-substituted bis-cyclometalated Ir(III) complexes with a picolinic acid as ancillary ligand

Yu, Hongcui; Liu, Chun; Lv, Xin; Xiu, Jinghai; Zhao, Jianzhang

doi:10.1016/j.dyepig.2017.05.056

Cited by 9 publications

(6 citation statements)

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“…The authors find out that the nanosensor is hypoxia-activated and able to detect cancer metastasis in vivo . The effect of substituents on the luminescence properties of cyclometalated Ir(III) complexes has been independently studied by Liu (Yu et al, 2017 ) and Yang (Wang et al, 2017 ). It has been reported that the presence of F atoms on large conjugated aromatic ligands improved the O 2 sensing performance of their Ir(III) complexes (Yu et al, 2017 ).…”

Section: Optical Sensing Approaches: the Role Of Oxygen Quenchingmentioning

confidence: 99%

“…The effect of substituents on the luminescence properties of cyclometalated Ir(III) complexes has been independently studied by Liu (Yu et al, 2017 ) and Yang (Wang et al, 2017 ). It has been reported that the presence of F atoms on large conjugated aromatic ligands improved the O 2 sensing performance of their Ir(III) complexes (Yu et al, 2017 ). DFT calculations suggested that such structural modifications increase the collision probability between the excited electrons of the Ir complexes and O 2 molecules resulting in a phosphorescence emission efficiently quenched by O 2 .…”

Section: Optical Sensing Approaches: the Role Of Oxygen Quenchingmentioning

confidence: 99%

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Oxygen Sensing, Hypoxia Tracing and in Vivo Imaging with Functional Metalloprobes for the Early Detection of Non-communicable Diseases

2018

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Hypoxia has been identified as one of the hallmarks of tumor environments and a prognosis factor in many cancers. The development of ideal chemical probes for imaging and sensing of hypoxia remains elusive. Crucial characteristics would include a measurable response to subtle variations of pO2 in living systems and an ability to accumulate only in the areas of interest (e.g., targeting hypoxia tissues) whilst exhibiting kinetic stabilities in vitro and in vivo. A sensitive probe would comprise platforms for applications in imaging and therapy for non-communicable diseases (NCDs) relying on sensitive detection of pO2. Just a handful of probes for the in vivo imaging of hypoxia [mainly using positron emission tomography (PET)] have reached the clinical research stage. Many chemical compounds, whilst presenting promising in vitro results as oxygen-sensing probes, are facing considerable disadvantages regarding their general application in vivo. The mechanisms of action of many hypoxia tracers have not been entirely rationalized, especially in the case of metallo-probes. An insight into the hypoxia selectivity mechanisms can allow an optimization of current imaging probes candidates and this will be explored hereby. The mechanistic understanding of the modes of action of coordination compounds under oxygen concentration gradients in living cells allows an expansion of the scope of compounds toward in vivo applications which, in turn, would help translate these into clinical applications. We summarize hereby some of the recent research efforts made toward the discovery of new oxygen sensing molecules having a metal-ligand core. We discuss their applications in vitro and/or in vivo, with an appreciation of a plethora of molecular imaging techniques (mainly reliant on nuclear medicine techniques) currently applied in the detection and tracing of hypoxia in the preclinical and clinical setups. The design of imaging/sensing probe for early-stage diagnosis would longer term avoid invasive procedures providing platforms for therapy monitoring in a variety of NCDs and, particularly, in cancers.

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Section: Optical Sensing Approaches: the Role Of Oxygen Quenchingmentioning

confidence: 99%

Section: Optical Sensing Approaches: the Role Of Oxygen Quenchingmentioning

confidence: 99%

Oxygen Sensing, Hypoxia Tracing and in Vivo Imaging with Functional Metalloprobes for the Early Detection of Non-communicable Diseases

2018

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“…13 C{ 1 H} NMR (100 MHz, acetone-d 6 ) δ (ppm) 171. 8,171.4 (d,J = 4.3 Hz),170.9 (d,J = 3.0 Hz),169.1 (dd,J = 11.2,238.3 Hz),168.8 (dd,J = 11.2,245.1 Hz),159.9 (dd,J = 12.5,238.7 Hz),159.7 (dd,J = 12.1,238.5 Hz),151.6,149.2,139.7,129.5,128.4,125.1 (d,J = 8.9 Hz),124.8 (d,J = 9.1 Hz), 127.9, 124.1 (q, J = 272.1 Hz), 122.5 (q, J = 271.8 = Hz), 122.4,122.1,120.6,120.3,109.1 (dd,J = 3.8,22.2 Hz),108.7 (dd,J = 3.8,22.0 Hz),105.6 (dd,J = 24.9,62.0 Hz),105.6 (dd,J = 2.2,24.8 Hz). MALDI HRMS for C 30 H 15 N 3 F 10…”

Section: ■ Conclusionmentioning

confidence: 99%

Exploiting the Reactivity of Fluorinated 2-Arylpyridines in Pd-Catalyzed C–H Bond Arylation for the Preparation of Bright Emitting Iridium(III) Complexes

et al. 2020

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Pd-catalyzed C-H bond arylation applied to 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine (1) and 2-(3,5-difluorophenyl)-5-(trifluoromethyl)pyridine (5) allows the access to two families of Ir(III) complexes, charge-neutral and cationic species. The reaction is regioselective since only the C3-or C4-position of the fluorinated phenyl ring of 1 or 5 is readily functionalized -namely the C-H bond flanked by the two fluorine atoms which is the most acidic -which allows the electronic control of the reactive site. A range of electron-withdrawing (CN, CO 2 Et, C(O)Me) substituents on the aryl group has been incorporated leading to the pro-ligands (Ar-2,4-dFppy; 2, Ar = p-C 6 H 4 -CN; 3, Ar = p-C 6 H 4 -CO 2 Et; 4, Ar = p-C 6 H 4 -C(O)Me; and Ar-3,5-dFppy; 6, Ar = p-C 6 H 4 -CO 2 Et). The unsubstituted complexes F/G-1 and F/G-5 featuring 1 and 5 respectively, as C^N ligands are used as reference complexes. The families of five charge-neutral [Ir(C^N) 2 (N^O)] complexes (C^N is 2-(5-aryl-(4,6-difluorophenyl)-5-(trifluoromethyl)pyridinato (F2-F4), and 2-(4-aryl-(3,5-difluorophenyl)-5-(trifluoromethyl)pyridinato (F5-F6), N^O = 2-picolinate] and five cationic [Ir(C^N) 2 (N^N)]PF 6 complexes [N^N = dmbpy is 4,4'-dimethyl-2,2'-bipyridine](G2-G6) were synthesized and their structural and photophysical properties studied with comparison to the unsubstituted analogues used as reference complexes. The appended aryl group provides large steric bulk as the biaryl fragment is twisted as shown by the X-ray crystal structures of F2, F5, F6, G3 and G5. These latter complexes display a wide variety of different Ir…Ir intermetallic distances in crystals, from 8.150 Å up to 15.034 Å. Moreover, the impact on the emission energy is negligible, as a result of the breaking of the conjugation between the two aryl groups. Charge-neutral complexes [Ir(C^N) 2 (N^O)] (N^O = 2picolinate) show bright luminescence: F2-F4 (λ em = 495-499 nm) are blue-green emitters whereas F5 and F6 (λ em = 537, 544 nm), where the fluorine substituents are located at the C3-and C5-positions, emit in the green region of the visible spectrum. In all cases, a unitary photoluminescence quantum yield is found. The improvement of  might be explained by an increase of the radiative rate constant due to a higher degree of rigidity of these congested molecules, compared to the unsubstituted complex F1. The same trends are observed for the family of complexes G. Complexes G1-G4 exhibit blue photoluminescence, and G5 and G6 leads to a red-shifted emission band, as also found for the related complexes F5 and F6 due to the similar fluorine substitution pattern. Their emission quantum yields are remarkably high for charged complexes in CH 2 Cl 2 solution. These results showed that Pd-catalyzed C-H bond arylation is a valuable synthetic approach for designing efficient emitters with tunable photophysical properties.

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“…A series of platinum(II) and iridium(III) complexes as efficient OSPs have been synthesized and investigated. 5,[37][38][39][40][41][42] In this paper, a new diphenylamino (DPA)-substituted cationic bis-cyclometalated Ir(III) complex with AIPE properties was synthesized, which was used to explore the effects of the DPA group on the photophysical and electrochemical properties of the corresponding Ir(III) complex. In addition, the oxygen sensitivity and operational stability of the Ir(III) complex were studied.…”

Section: Introductionmentioning

confidence: 99%

A diphenylamino-substituted cationic cyclometalated Ir(iii) complex: its aggregation-induced phosphorescent emission and oxygen sensing properties

Wang

Gao

Liu

et al. 2019

Mater. Chem. Front.

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Effect of substituents on properties of diphenylphosphoryl-substituted bis-cyclometalated Ir(III) complexes with a picolinic acid as ancillary ligand

Cited by 9 publications

References 50 publications

Oxygen Sensing, Hypoxia Tracing and in Vivo Imaging with Functional Metalloprobes for the Early Detection of Non-communicable Diseases

Oxygen Sensing, Hypoxia Tracing and in Vivo Imaging with Functional Metalloprobes for the Early Detection of Non-communicable Diseases

Exploiting the Reactivity of Fluorinated 2-Arylpyridines in Pd-Catalyzed C–H Bond Arylation for the Preparation of Bright Emitting Iridium(III) Complexes

A diphenylamino-substituted cationic cyclometalated Ir(iii) complex: its aggregation-induced phosphorescent emission and oxygen sensing properties

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