Long-range LMCT coupling in Eu(III) coordination polymers for an effective molecular luminescent thermometer.

A design for an effective molecular luminescent thermometer based on long-range electronic coupling in lanthanide coordination polymers is proposed. The coordination polymers are composed of lanthanide ions Eu(III) and Gd(III), three anionic ligands (hexafluoroacetylacetonate), and a chrysene-based phosphine oxide bridges (6,12-bis(diphenylphosphoryl)chrysene). The zig-zag orientation of the single polymer chains induces the formation of packed coordination structures containing multiple sites for CH-F intermolecular interactions, resulting in thermal stability above 350 ˚C. The electronic coupling is controlled by changing the concentration of the Gd(III) ion in the Eu(III)-Gd(III) polymer. The emission quantum yield and the maximum relative temperature sensitivity ( S m ) of emission lifetimes for the Eu(III)-Gd(III) polymer (Eu:Gd = 1:1, Φ tot = 52%, S m = 3.73% K -1 ) were higher than those for the pure Eu(III) coordination polymer ( Φ tot = 36%, S m = 2.70% K -1 ), respectively. Enhanced temperature sensing properties are caused by control of long-range electronic coupling based on phosphine oxide with chrysene framework.

[1]  Taku Nonomura,et al.  Characteristic Evaluation of Chameleon Luminophore Dispersed in Polymer , 2020, Sensors.

[2]  T. Nakanishi,et al.  The Role of π-f Orbital Interactions in Eu(III) Complexes for an Effective Molecular Luminescent Thermometer. , 2020, Inorganic chemistry.

[3]  T. Nakanishi,et al.  Stacked nanocarbon photosensitizer for efficient blue light excited Eu(III) emission , 2020, Communications Chemistry.

[4]  N. Inada,et al.  Temperature imaging using a cationic linear fluorescent polymeric thermometer and fluorescence lifetime imaging microscopy , 2019, Nature Protocols.

[5]  Dacheng Li,et al.  Tunable Light Emission and Multiresponsive Luminescent Sensitivities in Aqueous Solutions of Two Series of Lanthanide Metal-Organic Frameworks Based on Structurally Related Ligands. , 2019, ACS applied materials & interfaces.

[6]  L. Carlos,et al.  Lanthanide‐Based Thermometers: At the Cutting‐Edge of Luminescence Thermometry , 2018, Advanced Optical Materials.

[7]  Masanori Yamamoto,et al.  Ligand-Assisted Back Energy Transfer in Luminescent TbIII Complexes for Thermosensing Properties. , 2018, Chemistry.

[8]  L. Liz‐Marzán,et al.  Guiding Rules for Selecting a Nanothermometer , 2018 .

[9]  T. Nakanishi,et al.  A Luminescent Dinuclear EuIII /TbIII Complex with LMCT Band as a Single-Molecular Thermosensor. , 2018, Chemistry.

[10]  Masato Kobayashi,et al.  Enhanced Luminescence of Asymmetrical Seven‐Coordinate EuIII Complexes Including LMCT Perturbation , 2017 .

[11]  Xinhui Zhou,et al.  Visible‐Light Excited Luminescent Thermometer Based on Single Lanthanide Organic Frameworks , 2016 .

[12]  M. Dramićanin.  Sensing temperature via downshifting emissions of lanthanide-doped metal oxides and salts. A review , 2016, Methods and applications in fluorescence.

[13]  L. Carlos,et al.  Lanthanide Organic Framework Luminescent Thermometers. , 2016, Chemistry.

[14]  Chung‐Hsin Lu,et al.  Structural evaluations and temperature dependent photoluminescence characterizations of Eu3+-activated SrZrO3 hollow spheres for luminescence thermometry applications , 2016, Scientific Reports.

[15]  K. Binnemans.  Interpretation of europium(III) spectra , 2015 .

[16]  W. M. Faustino,et al.  The Role of the Ligand-to-Metal Charge-Transfer State in the Dipivaloylmethanate-Lanthanide Intramolecular Energy Transfer Process , 2015 .

[17]  Yuanjing Cui,et al.  Lanthanide metal-organic frameworks for luminescent sensing and light-emitting applications , 2014 .

[18]  O. Wolfbeis,et al.  Luminescent probes and sensors for temperature. , 2013, Chemical Society reviews.

[19]  Takayuki Nakanishi,et al.  Chameleon luminophore for sensing temperatures: control of metal-to-metal and energy back transfer in lanthanide coordination polymers. , 2013, Angewandte Chemie.

[20]  Luís D Carlos,et al.  Thermometry at the nanoscale. , 2015, Nanoscale.

[21]  Y. Harada,et al.  Intracellular temperature mapping with a fluorescent polymeric thermometer and fluorescence lifetime imaging microscopy , 2012, Nature Communications.

[22]  Zhiyong Guo,et al.  A luminescent mixed-lanthanide metal-organic framework thermometer. , 2012, Journal of the American Chemical Society.

[23]  W. M. Faustino,et al.  Photoluminescence of europium(III) dithiocarbamate complexes: electronic structure, charge transfer and energy transfer. , 2006, The journal of physical chemistry. A.

[24]  S. Alvarez,et al.  The rich stereochemistry of eight-vertex polyhedra: a continuous shape measures study. , 2005, Chemistry.

[25]  P. Lincoln,et al.  Three-State Light Switch of [Ru(phen)2dppz]2+: Distinct Excited-State Species with Two, One, or No Hydrogen Bonds from Solvent , 2004 .

[26]  J. Verhoeven,et al.  The emission spectrum and the radiative lifetime of Eu3+ in luminescent lanthanide complexes , 2002 .

[27]  C. Meyers,et al.  Effect of Ligand Deuteration on the Decay of Eu3+(5D0) in Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)europium(III) , 1998 .

[28]  W. Weaver,et al.  FLUORESCENCE LIFETIME MEASUREMENTS AND SPECTRAL ANALYSIS OF ADAMANTYLDIAZIRINE , 1997 .