Self‐Assembly between Dicarboxylate Ions and Dinuclear Lanthanide Complexes: A Surprisingly Complicated Problem

The association between dinuclear lanthanide complexes and dicarboxylate guests has been studied to elucidate the factors that influence the self-assembly of these ternary structures. The self-assembly between α,α′-bis(Eu·DO3A)-m-xylyl (H3DO3A = 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) host complexes and dicarboxylate guests and the association of a dinicotinate guest and an α,α′-bis(Ln·DO3A)-3,5-dimethylpyridine host in water were demonstrated, and the study of lanthanide-mediated self-assembly and the methods used to investigate the self-assembly are discussed in detail. Furthermore, the self-assembly has been extended to involve five ions from across the lanthanide series, namely, Nd3+, Eu3+, Tb3+, Dy3+ and Yb3+. The self-assembly process, measured by the association constant Ka, is independent of the nature of the lanthanide centre but it is highly solvent dependent. The association constants between a given host–guest pair vary by several orders of magnitude when determined in methanol, methanol/water and water. We conclude that although a lanthanide-centred self-assembly process can be controlled through design, the strength of the association can only be rationalised after the event. The multiple parameters involved in the determination of the value of the association constant appear to be dominated by the solvation contribution to a degree that specific and general solvation has to be understood before we can fully rationalise the association between dinuclear lanthanide complexes and dicarboxylate guests.

[1]  R. J. Aarons,et al.  Using remote substituents to control solution structure and anion binding in lanthanide complexes. , 2013, Chemistry.

[2]  T. Sørensen,et al.  Ternary self-assemblies in water: forming a pentanuclear ReLn4 assembly by association of binuclear lanthanide binding pockets with fac-Re(CO)3(dinicotinate)2Cl. , 2013, Dalton transactions.

[3]  C. Piguet,et al.  Monitoring helical twists and effective molarities in dinuclear triple-stranded lanthanide helicates. , 2013, Dalton transactions.

[4]  Wei Xu,et al.  On structure and bonding of lanthanoid trifluorides LnF3 (Ln = La to Lu). , 2013, Physical chemistry chemical physics : PCCP.

[5]  W. Wernsdorfer,et al.  Subcomponent self-assembly of rare-earth single-molecule magnets. , 2013, Inorganic chemistry.

[6]  D. Parker,et al.  Anion binding in water at lanthanide centres: from structure and selectivity to signalling and sensing. , 2013, Chemical Society reviews.

[7]  Michael Hietschold,et al.  Metastable β-Bi2O3 nanoparticles with high photocatalytic activity from polynuclear bismuth oxido clusters. , 2013, Dalton transactions.

[8]  T. Sørensen,et al.  Preparation and study of an f,f,f',f'' covalently linked tetranuclear hetero-trimetallic complex - a europium, terbium, dysprosium triad. , 2013, Chemical communications.

[9]  Jason J. Davis,et al.  Reversible recruitment and emission of DO3A-derived lanthanide complexes at ligating molecular films on gold. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[10]  P. Beer,et al.  Self-assembly between dicarboxylate ions and binuclear europium complexes: moving to water-pH dependence and effects of buffers. , 2013, Dalton transactions.

[11]  D. Parker,et al.  Lanthanide complexes as chiral probes exploiting circularly polarized luminescence. , 2012, Chemical Society reviews.

[12]  T. Gunnlaugsson,et al.  Formation of luminescent terbium(III) self-assemblies from pyridyl bis-amidothioureas based ligands in MeOH and in water-DMSO solutions and their use in anion sensing application. , 2012, Organic & biomolecular chemistry.

[13]  R. Pal,et al.  Live cell imaging of lysosomal pH changes with pH responsive ratiometric lanthanide probes. , 2012, Chemical communications.

[14]  T. Sørensen,et al.  Self-assembly between dicarboxylate ions and a binuclear europium complex: formation of stable adducts and heterometallic lanthanide complexes. , 2011, Dalton transactions.

[15]  A. Kenwright,et al.  Lanthanide complexes of DOTA monoamide derivatives bearing an isophthalate pendent arm. , 2011, Dalton transactions.

[16]  M. Woods,et al.  Analysis of the conformational behavior and stability of the SAP and TSAP isomers of lanthanide(III) NB-DOTA-type chelates. , 2011, Inorganic chemistry.

[17]  M. Botta,et al.  Properties, solution state behavior, and crystal structures of chelates of DOTMA. , 2011, Inorganic chemistry.

[18]  R. Pal,et al.  Evidence for the optical signalling of changes in bicarbonate concentration within the mitochondrial region of living cells. , 2011, Chemical communications.

[19]  A. Sherry,et al.  The population of SAP and TSAP isomers in cyclen-based lanthanide(III) chelates is substantially affected by solvent. , 2010, Inorganic chemistry.

[20]  P. Ballester.  Anion binding in covalent and self-assembled molecular capsules. , 2010, Chemical Society reviews.

[21]  D. Parker,et al.  Development of responsive lanthanide probes for cellular applications. , 2010, Current opinion in chemical biology.

[22]  A. Kenwright,et al.  Bimetallic Lanthanide Complexes Derived from Macrocycle‐Appended m‐Xylyl Derivatives: Synthesis and Spectroscopic Properties , 2009 .

[23]  P. Stang,et al.  Self-organization in coordination-driven self-assembly. , 2009, Accounts of chemical research.

[24]  R. Pal,et al.  A europium luminescence assay of lactate and citrate in biological fluids. , 2009, Organic & biomolecular chemistry.

[25]  R. Pal,et al.  Cell-penetrating metal complex optical probes: targeted and responsive systems based on lanthanide luminescence. , 2009, Accounts of chemical research.

[26]  Susan J. Quinn,et al.  Recent developments in the field of supramolecular lanthanide luminescent sensors and self-assemblies , 2008 .

[27]  R. Scopelliti,et al.  Multicomponent assembly of boronic acid based macrocycles and cages. , 2008, Angewandte Chemie.

[28]  T. Gunnlaugsson,et al.  Recent advances in the formation of luminescent lanthanide architectures and self-assemblies from structurally defined ligands. , 2007, Organic & biomolecular chemistry.

[29]  T. Gunnlaugsson,et al.  A dinuclear lanthanide complex for the recognition of bis(carboxylates): formation of terbium(III) luminescent self-assembly ternary complexes in aqueous solution. , 2006, Inorganic chemistry.

[30]  K. Douglas,et al.  Self-assembly of heterobimetallic d-f hybrid complexes: sensitization of lanthanide luminescence by d-block metal-to-ligand charge-transfer excited states. , 2004, Journal of the American Chemical Society.

[31]  D. Parker.  Excitement in f block: structure, dynamics and function of nine-coordinate chiral lanthanide complexes in aqueous media. , 2004, Chemical Society reviews.

[32]  Horst Puschmann,et al.  Being excited by lanthanide coordination complexes: aqua species, chirality, excited-state chemistry, and exchange dynamics. , 2002, Chemical reviews.

[33]  J. Bünzli,et al.  Lanthanide-containing molecular and supramolecular polymetallic functional assemblies. , 2002, Chemical reviews.

[34]  P. Kuzmič,et al.  Program DYNAFIT for the analysis of enzyme kinetic data: application to HIV proteinase. , 1996, Analytical biochemistry.

[35]  G. Bernardinelli,et al.  The First Self‐Assembled Dinuclear Triple‐Helical Lanthanide Complex: Synthesis and Structure , 1992 .

[36]  Frederick S. Richardson,et al.  Terbium(III) and europium(III) ions as luminescent probes and stains for biomolecular systems , 1982 .

[37]  S. Gottschalk,et al.  Responsive imaging probes for metabotropic glutamate receptors , 2012 .

[38]  Christopher M. Andolina,et al.  Luminescence Resonance Energy Transfer in Heterodinuclear LnIII Complexes for Sensing Biologically Relevant Anions , 2011 .

[39]  William R. Dichtel,et al.  Complexation between methyl viologen (paraquat) bis(hexafluorophosphate) and dibenzo[24]crown-8 revisited. , 2009, Chemistry.

[40]  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 .

[41]  C. Jørgensen,et al.  Hypersensitive pseudoquadrupole transitions in lanthanides , 1964 .