Near‐IR Luminescent Yb^III Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Abstract

Oxygen-sensitive and near-infrared( NIR) luminescent Yb III coordination polymers incorporatingl igandsb ased on pyrene derivatives were synthesized:Y b III -TBAPy and Yb III -TIAPy (TBAPy:1 ,3,6,8-tetrakis(p-benzoate)pyrene;T IAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of thesem aterials have been characterized by means of electrospray ionization mass spectrometry,X -ray diffractiona nalysis, and thermogravimetric analysis. Moreover,t he porouss tructure of Yb III -TIAPy has been evaluated by measuring its N 2 adsorption isotherm.T he NIR lumines-cence properties of Yb III -TBAPy and Yb III -TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb III -TIAPy exhibitedh igh thermals tability (with ad ecomposition temperature of 400 8C), intensel uminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb III coordination polymers prepared using pyrene derivatives could have applications in novel thermostable oxygen sensors.

An Europium (III) Luminophore with Pressure‐Sensing Units: Effective Back Energy Transfer in Coordination Polymers with Hexadentate Porous Stable Networks

“…Using the ideal gas law, the amount nitrogen adsorption amount at a pressure (P) of 101.25 kPa and a temperature (T) of 273.15 K (that is, STP conditions) was calculated using the ideal gas constant (R) of 8.31 J K −1 mol −1 and a volume (V) of 64.69 cm 3 (p/p 0 =1.0). The amount of nitrogen adsorption was evaluated to be 8.4×10 −2 cm 3 g −1 , which is similar to that of previously reported porous Yb III coordination polymer with octadentate pyrene units (8.0×10 −2 cm 3 g −1 ) . The specific surface area of Eu III ‐hcpt was estimated using Brunauer‐Emmet‐Teller (BET) calculation as 407 m 2 g −1 (Figure S3).…”

“…Amao presented the first PSP using luminescent Eu III complex based on the O 2 ‐quenching in the T 1 state of the photosensitized ligand . We have reported oxygen‐sensitive near‐infrared luminophores composed of porous Yb III coordination porous networks for PSPs . The O 2 ‐sensitive metal complex is expected to be useful for PSP applications in aerodynamics.…”

“…However, general transition‐metal complexes lead to a significant decrease of their phosphorescence lifetimes in the presence of small amounts of O 2 , which results in the formation of non‐emission compounds in air. According to the luminescent lanthanide complexes, their 4f–4f emission lifetimes are independent of O 2 ‐quenching in the T 1 state of the photosensitizer . Novel time‐resolved analysis of phosphorescence under a highly concentration of O 2 environments is thus required.…”

“…The low‐lying energy level of the photosensitization ligand is much close to that of the emitting level of the Eu III ion ( 5 D 0 : 17,200 cm −1 ), which promotes BEnT with activation energy from the excited Eu III complex. Multi‐dentate coordination sites should also be attached in the photosensitization triphenylene unit for the formation of a thermo‐stable structure . The multidentate coordination sites are expected to construct the thermo‐stable tight packing networks and an O 2 ‐active porous structure in the Eu III coordination polymer.…”

Pyrene-based metal organic frameworks: from synthesis to applications

“…154 The origin of the luminescence in MOFs can be associated with a variety of mechanisms due to the structural diversity of MOFs. 155 This can include ligand-based emission, 66 metal-based emission, 67,89 emission due to excimer formation, 156 or guest induced emission. 155,157 Pyrene-based MOFs have been attractive for sensing applications due to the fluorescence properties of pyrene.…”