PMID- 31553597
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20191015
LR  - 20191015
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 58
IP  - 19
DP  - 2019 Oct 7
TI  - Imidodiphosphonate Ligands for Enhanced Sensitization and Shielding of Visible 
      and Near-Infrared Lanthanides.
PG  - 13268-13275
LID - 10.1021/acs.inorgchem.9b02090 [doi]
AB  - The design of coordination sites around lanthanide ions has a strong impact on 
      the sensitization of their luminescent signal. An imidodiphosphonate anionic 
      binding site is attractive as it can be functionalized with "remote" sensitizer 
      units, such as phenoxy moieties, namely, HtpOp, accompanied by an increased 
      distance of the lanthanide from the ligand high-energy stretching vibrations 
      which quench the luminescence signal, hence providing flexible shielding of the 
      lanthanide. We report the formation and isolation of Ln(tpOp)(3) complexes where 
      Ln = Er, Gd, Tb, Dy, Eu, and Yb and the Y(tpOp)(3) diamagnetic analogue. The 
      complexes are formed from reaction of KtpOp and the corresponding LnCl(3).6H(2)O 
      salt either by titration and in situ formation or by mixing and isolation. All 
      complexes are seven-coordinated by three tpOp ligand plus one ethanol molecule, 
      except for Yb(tpOp)(3) which has no solvent coordinated. Phosphorus NMR shows 
      characteristic shifts to support the coordination of the lanthanide complexes. 
      The complexes display visible and near-infrared luminescence with long lifetimes 
      even for the near-infrared complexes which range from 3.3 mus for Nd(tpOp)(3) to 
      20 mus for Yb(tpOp)(3). The ligand shows more efficient sensitization than the 
      imidodiphosphinate analogues for all lanthanide complexes with a notable quantum 
      yield of the Tb(tpOp)(3) complex at 45%. We attribute this to the properties of 
      the remote sensitizer unit and its positioning further away from the lanthanide, 
      eliminating quenching of high energy C-H vibrations from the ligand shell. 
      Calculations of the ligand shielding support the photophysical properties of the 
      complexes. These results suggest that these binding sites are promising in the 
      further development of the lanthanide complexes in optoelectronic devices for 
      telecommunications and new light emitting materials.
FAU - Davis, Dita
AU  - Davis D
AD  - School of Chemistry , The University of Birmingham , Edgbaston B15 2TT , United 
      Kingdom.
FAU - Carrod, Andrew J
AU  - Carrod AJ
AD  - School of Chemistry , The University of Birmingham , Edgbaston B15 2TT , United 
      Kingdom.
FAU - Guo, Zhilin
AU  - Guo Z
AD  - School of Chemistry , The University of Birmingham , Edgbaston B15 2TT , United 
      Kingdom.
AD  - Department of Chemistry , Southern University of Science and Technology , 
      Shenzhen 518055 , China.
FAU - Kariuki, Benson M
AU  - Kariuki BM
AUID- ORCID: 0000-0002-8658-3897
AD  - School of Chemistry , Cardiff University , Cardiff CF10 3AT , United Kingdom.
FAU - Zhang, Yuan-Zhu
AU  - Zhang YZ
AUID- ORCID: 0000-0002-1676-2427
AD  - Department of Chemistry , Southern University of Science and Technology , 
      Shenzhen 518055 , China.
FAU - Pikramenou, Zoe
AU  - Pikramenou Z
AUID- ORCID: 0000-0002-6001-1380
AD  - School of Chemistry , The University of Birmingham , Edgbaston B15 2TT , United 
      Kingdom.
LA  - eng
PT  - Journal Article
DEP - 20190925
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
SB  - IM
EDAT- 2019/09/26 06:00
MHDA- 2019/09/26 06:01
CRDT- 2019/09/26 06:00
PHST- 2019/09/26 06:00 [pubmed]
PHST- 2019/09/26 06:01 [medline]
PHST- 2019/09/26 06:00 [entrez]
AID - 10.1021/acs.inorgchem.9b02090 [doi]
PST - ppublish
SO  - Inorg Chem. 2019 Oct 7;58(19):13268-13275. doi: 10.1021/acs.inorgchem.9b02090. 
      Epub 2019 Sep 25.