Molecular Upconversion in Water in Heteropolynuclear Supramolecular Tb/Yb Assemblies.

Piling up excited states to reach upconversion (UC) is severely restricted by vibrational quenching mechanisms, especially when one looks at discrete molecular entities in solution. By carefully controlling the supramolecular assembly processes resulting from the strong electrostatic interactions between negatively charged Yb complexes and Tb3+ cations in aqueous solutions, we engineered the formation of heteropolynuclear complexes of [(YbL)2Tb x] compositions ( x = 1 and 2). These edifices display a phenomenon of cooperative photosensitization UC with green emission of the Tb cations upon NIR excitation at 980 nm in the Yb absorption band. The photophysical properties of the complexes were carefully investigated by steady-state and time-resolved luminescence experiments in D2O, allowing one to quantify the impact of the composition and pD of the solution on the emission intensity as well as clarifying the exact cooperative photosensitization upconversion mechanism. Using optimized conditions, the energy transfer UC process could be observed for the first time in nondeuterated water with discrete molecular compounds.

[1]  Loïc J Charbonnière,et al.  Bringing upconversion down to the molecular scale. , 2018, Dalton transactions.

[2]  S. Cianférani,et al.  Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines. , 2018, Inorganic chemistry.

[3]  Juan Tang,et al.  Highly luminescent, biocompatible ytterbium(iii) complexes as near-infrared fluorophores for living cell imaging† †Electronic supplementary information (ESI) available: Detailed photophysical and cell experiment data; 1H and 19F NMR spectra, UV-visible absorption spectra; IR spectra and MS spectra. , 2018, Chemical science.

[4]  Ka‐Leung Wong,et al.  Upconverted Photosensitization of Tb Visible Emission by NIR Yb Excitation in Discrete Supramolecular Heteropolynuclear Complexes. , 2017, Journal of the American Chemical Society.

[5]  S. Cianférani,et al.  Step by Step Assembly of Polynuclear Lanthanide Complexes with a Phosphonated Bipyridine Ligand. , 2016, Inorganic chemistry.

[6]  W. Wong,et al.  Room temperature molecular up conversion in solution , 2016, Nature Communications.

[7]  A. Hauser,et al.  Taming Lanthanide-Centered Upconversion at the Molecular Level. , 2016, Inorganic chemistry.

[8]  P. Beer,et al.  Substituent effects on fluoride binding by lanthanide complexes of DOTA-tetraamides. , 2016, Dalton transactions.

[9]  M. Seitz,et al.  The Radiative Lifetime in Near-IR-Luminescent Ytterbium Cryptates: The Key to Extremely High Quantum Yields. , 2015, Angewandte Chemie.

[10]  P. Beer,et al.  Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+ in Aqueous Solution , 2015, Angewandte Chemie.

[11]  C. Platas‐Iglesias,et al.  Toward the Prediction of Water Exchange Rates in Magnetic Resonance Imaging Contrast Agents: A Density Functional Theory Study. , 2015, The journal of physical chemistry. A.

[12]  M. Botta,et al.  Importance of outer-sphere and aggregation phenomena in the relaxation properties of phosphonated gadolinium complexes with potential applications as MRI contrast agents. , 2015, Chemistry.

[13]  Wei Zheng,et al.  Lanthanide-doped upconversion nano-bioprobes: electronic structures, optical properties, and biodetection. , 2015, Chemical Society reviews.

[14]  Artur Bednarkiewicz,et al.  Upconverting nanoparticles: assessing the toxicity. , 2015, Chemical Society reviews.

[15]  A. Hauser,et al.  Smaller than a nanoparticle with the design of discrete polynuclear molecular complexes displaying near-infrared to visible upconversion. , 2015, Dalton transactions.

[16]  G. Sheldrick.  Crystal structure refinement with SHELXL , 2015, Acta crystallographica. Section C, Structural chemistry.

[17]  T. Soukka,et al.  Photon Upconversion in a Molecular Lanthanide Complex in Anhydrous Solution at Room Temperature , 2014 .

[18]  P. Prasad,et al.  Upconversion Nanoparticles: Design, Nanochemistry, and Applications in Theranostics , 2014, Chemical reviews.

[19]  A. Hauser,et al.  Near-Infrared to Visible Light-Upconversion in Molecules: From Dream to Reality , 2013 .

[20]  Louis J. Farrugia,et al.  WinGX and ORTEP for Windows: an update , 2012 .

[21]  M. Elhabiri,et al.  Highly relaxing gadolinium based MRI contrast agents responsive to Mg2+ sensing. , 2012, Chemical communications.

[22]  H. Tam,et al.  Water-soluble mitochondria-specific ytterbium complex with impressive NIR emission. , 2011, Journal of the American Chemical Society.

[23]  A. Hauser,et al.  Near-infrared→visible light upconversion in a molecular trinuclear d-f-d complex. , 2011, Angewandte Chemie.

[24]  Helmut Schäfer,et al.  Upconverting nanoparticles. , 2011, Angewandte Chemie.

[25]  Caroline Bischof,et al.  Quantification of C-H quenching in near-IR luminescent ytterbium and neodymium cryptates. , 2010, Journal of the American Chemical Society.

[26]  M. Elhabiri,et al.  Formation of very stable and selective Cu(II) complexes with a non-macrocyclic ligand: can basicity rival pre-organization? , 2010, Dalton transactions.

[27]  S. Eliseeva,et al.  Lanthanide Luminescence for Functional Materials and Bio‐Sciences , 2010 .

[28]  Hiroshi Maeda,et al.  Tumor-selective delivery of macromolecular drugs via the EPR effect: background and future prospects. , 2010, Bioconjugate chemistry.

[29]  J. Bünzli,et al.  Lanthanide luminescence for functional materials and bio-sciences. , 2010, Chemical Society reviews.

[30]  Jian Zhang,et al.  Pyridine-based lanthanide complexes: towards bimodal agents operating as near infrared luminescent and MRI reporters. , 2008, Chemical communications.

[31]  S. Alvarez,et al.  Polyhedral structures with an odd number of vertices: nine-coordinate metal compounds. , 2008, Chemistry.

[32]  G. Scuseria,et al.  Gaussian 03, Revision E.01. , 2007 .

[33]  J. Tomasi,et al.  Quantum mechanical continuum solvation models. , 2005, Chemical reviews.

[34]  Aldo Roda,et al.  Engineering of highly luminescent lanthanide tags suitable for protein labeling and time-resolved luminescence imaging. , 2004, Journal of the American Chemical Society.

[35]  F. Auzel.  Upconversion and anti-Stokes processes with f and d ions in solids. , 2004, Chemical reviews.

[36]  Joop A. Peters,et al.  X-ray Crystal Structure of a Sodium Salt of [Gd(DOTP)]5: Implications for Its Second-Sphere Relaxivity and the 23Na NMR Hyperfine Shift Effects of [Tm(DOTP)]5- , 2003 .

[37]  G. Scuseria,et al.  Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids. , 2003, Physical review letters.

[38]  G. Palmisano,et al.  Designing Novel Contrast Agents for Magnetic Resonance Imaging. Synthesis and Relaxometric Characterization of three Gadolinium(III) Complexes Based on Functionalized Pyridine-Containing Macrocyclic Ligands , 2003 .

[39]  M. Botta,et al.  Structural variations across the lanthanide series of macrocyclic DOTA complexes: insights into the design of contrast agents for magnetic resonance imaging. , 2003, Inorganic chemistry.

[40]  H. U. G. ̈. del,et al.  Cooperative Yb 3 ¿-Tb 3 ¿ dimer excitations and upconversion in Cs 3 Tb 2 Br 9 : Yb , 2003 .

[41]  G M Salley,et al.  Phonon-assisted cooperative sensitization of Tb3+ in SrCl2:Yb, Tb , 2002 .

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

[43]  C. Piguet,et al.  Analysis of paramagnetic NMR spectra of triple-helical lanthanide complexes with 2,6-dipicolinic acid revisited: a new assignment of structural changes and crystal-field effects 25 years later. , 2002, Inorganic chemistry.

[44]  Rafael Valiente,et al.  Luminescence upconversion mechanisms in Yb3+–Tb3+ systems , 2001 .

[45]  P. Hermann,et al.  Complexes of tetraazacycles bearing methylphosphinic/phosphonic acid pendant arms with copper(II), zinc(II) and lanthanides(III). A comparison with their acetic acid analogues , 2001 .

[46]  Philippe Goldner,et al.  Towards rare-earth clustering control in doped glasses , 2001 .

[47]  D. Gamelin,et al.  Design of luminescent inorganic materials: new photophysical processes studied by optical spectroscopy. , 2000, Accounts of chemical research.

[48]  Markus P. Hehlen,et al.  Power dependence of upconversion luminescence in lanthanide and transition-metal-ion systems , 2000 .

[49]  A. Beeby,et al.  Non-radiative deactivation of the excited states of europium, terbium and ytterbium complexes by proximate energy-matched OH, NH and CH oscillators: an improved luminescence method for establishing solution hydration states , 1999 .

[50]  Jurriaan Huskens,et al.  Lanthanide induced shifts and relaxation rate enhancements , 1996 .

[51]  Qian Zhao,et al.  Analyzing Lanthanide-Induced Shifts in the NMR Spectra of Lanthanide(III) Complexes Derived from 1,4,7,10-Tetrakis(N,N-diethylacetamido)-1,4,7,10-tetraazacyclododecane , 1995 .

[52]  Maria Cristina Burla,et al.  SIR92 – a program for automatic solution of crystal structures by direct methods , 1994 .

[53]  M. Botta,et al.  Determination of metal–proton distances and electronic relaxation times in lanthanide complexes by nuclear magnetic resonance spectroscopy , 1992 .

[54]  Michael Dolg,et al.  Energy-adjusted pseudopotentials for the rare earth elements , 1989 .

[55]  W. Horrocks,et al.  Lanthanide ion probes of structure in biology. Laser-induced luminescence decay constants provide a direct measure of the number of metal-coordinated water molecules , 1979 .