Amine-templated polymeric lanthanide formates: synthesis, characterization, and applications in luminescence and magnetism.

The novel polymeric formates of general formula [(Fmd)Ln(III)(HCOO)(4)](∞) (Fmd(+) = NH(2)-CH(+)-NH(2); Ln = Eu (1), Gd (2), Tb (3), Dy (4)] were synthesized through solvothermal methods in formamide solutions. The compounds are isotructural; they crystallize in the orthorhombic C222(1) chiral space group. The coordination geometry at the metal centers is square antiprismatic (coordination number eight), with each formate ligand bridging adjacent lanthanide ions. The overall negative three-dimensional (3D) framework charge is balanced by the formamidinium cations sitting inside the channels along the a axis, forming extensive N-H···O hydrogen bonding with the surrounding cage. All the compounds have been characterized through single-crystal/powder X-ray diffraction, IR spectroscopy, and TG-MS analysis. Finally, their luminescence and magnetic properties have been assessed, leading to remarkable emission intensities, especially for the Tb(III) compound (Φ = 0.83), with corresponding lifetime decays in the micro (Dy) and millisecond (Tb, Eu) time scale. A weak but sizable antiferromagnetic interaction has been observed for the Gd(III) derivative.

[1]  M. Peruzzini,et al.  Amine-templated polymeric Mg formates: crystalline scaffolds exhibiting extensive hydrogen bonding , 2012 .

[2]  R. Sessoli.  Chilling with magnetic molecules. , 2012, Angewandte Chemie.

[3]  Zhengang Sun,et al.  Synthesis, Crystal Structures, and Luminescence and Magnetic Properties of 3D Chiral and Achiral Lanthanide Diphosphonates Containing Left- and Right-Handed Helical Chains , 2011 .

[4]  S. Quici,et al.  Synthesis and photophysical characterization of highly luminescent silica films doped with substituted 2-hydroxyphthalamide (IAM) terbium complexes. , 2011, Dalton transactions.

[5]  B. Liu,et al.  Chiral crystalline solids of ammonium-templated ErIII–formate frameworks assembled from three achiral acentric components , 2011 .

[6]  M. Peruzzini,et al.  Hydrogen uptake by {H[Mg(HCOO)3]⊃NHMe2}∞ and determination of its H2 adsorption sites through Monte Carlo simulations. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[7]  J. Alonso,et al.  Cryogenic magnetocaloric effect in a ferromagnetic molecular dimer. , 2011, Angewandte Chemie.

[8]  V. Blatov,et al.  Underlying nets in three-periodic coordination polymers: topology, taxonomy and prediction from a computer-aided analysis of the Cambridge Structural Database , 2011 .

[9]  B. Wang,et al.  Erbium-formate frameworks templated by diammonium cations: syntheses, structures, structural transition and magnetic properties. , 2011, Dalton transactions.

[10]  Heng Xu,et al.  Novel 3D lanthanide-organic frameworks with an unusual infinite nanosized ribbon [Ln3(μ3–OH)2(–CO2)6]+n (Ln = Eu, Gd, Dy): syntheses, structures, luminescence, and magnetic properties , 2011 .

[11]  O. Shekhah,et al.  MOF thin films: existing and future applications. , 2011, Chemical Society reviews.

[12]  B. Liu,et al.  A series of lanthanide-organic polymers incorporating nitrogen-heterocyclic and aliphatic carboxylate mixed-ligands: structures, luminescent and magnetic properties. , 2010, Dalton transactions.

[13]  J. Wosnitza,et al.  Spin relaxation and resonant phonon trapping in [Gd2(fum)3(H2O)4]s3H2O , 2010 .

[14]  E. Brechin,et al.  Recipes for enhanced molecular cooling. , 2010, Dalton transactions.

[15]  W. Wernsdorfer,et al.  New heterometallic [Mn(III)(4)Ln(III)(4)] wheels incorporating formate ligands. , 2010, Dalton transactions.

[16]  Daofeng Sun,et al.  An Open Neodymium−Organic Framework with the NbO Structure Type Based on Binuclear SBU Involved In Situ Generated Formate , 2010 .

[17]  Gianluca Accorsi,et al.  Design of luminescent lanthanide complexes: From molecules to highly efficient photo-emitting materials , 2010 .

[18]  U. Mueller,et al.  A mesoporous metal-organic framework. , 2009, Angewandte Chemie.

[19]  Song Gao,et al.  Magnetism and magnetocaloric effect in S = 7/2 Heisenberg antiferromagnet Gd2(fum)3(H2O)4·3H2O , 2009 .

[20]  Bin Zhao,et al.  A porous 3D heterometal-organic framework containing both lanthanide and high-spin Fe(ii) ions. , 2009, Chemical communications.

[21]  M. Kurmoo.  Magnetic metal-organic frameworks. , 2009, Chemical Society reviews.

[22]  Song Gao,et al.  Syntheses, structures and properties of seven isomorphous 1D Ln3+complexes Ln(BTA)(HCOO)(H2O)3 (H2BTA = bis(tetrazoly)amine, Ln = Pr, Gd, Eu, Tb, Dy, Er, Yb) and two 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr, Nd). , 2008, Dalton transactions.

[23]  A. Vindigni,et al.  Single chain magnets: where to from here? , 2008 .

[24]  M. O'keeffe,et al.  The Reticular Chemistry Structure Resource (RCSR) database of, and symbols for, crystal nets. , 2008, Accounts of chemical research.

[25]  M. Caporali,et al.  Phase Transitions and CO2 Adsorption Properties of Polymeric Magnesium Formate , 2008 .

[26]  Ai-Ling Cheng,et al.  Towards tuning the packing and entanglement of zigzag coordination chains by terminal ligands. , 2008, Dalton transactions.

[27]  S. Natarajan,et al.  The role of temperature on the structure and dimensionality of MOFs: an illustrative study of the formation of manganese oxy-bis(benzoate) structures. , 2007, Chemical communications.

[28]  H. Höppe,et al.  Systematic investigation of lanthanide phosphonatoethanesulfonate framework structures by high-throughput methods, Ln(O3P-C2H4-SO3)(H2O) (Ln=La-Dy). , 2007, Inorganic Chemistry.

[29]  Shoutian Zheng,et al.  Diversity of crystal structure with different lanthanide ions involving in situ oxidation-hydrolysis reaction. , 2007, Dalton transactions.

[30]  Daqiang Yuan,et al.  A blue luminescent inorganic–organic hybrid with infinite [Cd3(μ3-OH)2(μ2-Cl)2] connectivity , 2007 .

[31]  A. Jacobson,et al.  Solid Solution Precursors to Gadolinia-Doped Ceria Prepared via a Low-Temperature Solution Route , 2007 .

[32]  M. Zaworotko,et al.  Exciplex fluorescence as a diagnostic probe of structure in coordination polymers of Zn2+ and 4,4'-bipyridine containing intercalated pyrene and enclathrated aromatic solvent guests. , 2007, Journal of the American Chemical Society.

[33]  N. Tamai,et al.  Molecular distortion effect on ff-emission in a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline. , 2007, Chemphyschem : a European journal of chemical physics and physical chemistry.

[34]  X. Wang,et al.  Three Novel Cd(II) Metal−Organic Frameworks Constructed from Mixed Ligands of Dipyrido[3,2-d:2‘,3‘-f]quinoxaline and Benzene-dicarboxylate: From a 1-D Ribbon, 2-D Layered Network, to a 3-D Architecture , 2007 .

[35]  J. Veciana,et al.  Old materials with new tricks: multifunctional open-framework materials. , 2007, Chemical Society reviews.

[36]  C. Cahill,et al.  Exploring lanthanide luminescence in metal-organic frameworks: synthesis, structure, and guest-sensitized luminescence of a mixed europium/terbium-adipate framework and a terbium-adipate framework. , 2007, Inorganic chemistry.

[37]  M. Du,et al.  Molecular tectonics of mixed-ligand metal-organic frameworks: positional isomeric effect, metal-directed assembly, and structural diversification. , 2007, Inorganic chemistry.

[38]  E. Gutiérrez‐Puebla,et al.  Rare earth arenedisulfonate metal-organic frameworks: an approach toward polyhedral diversity and variety of functional compounds. , 2007, Inorganic chemistry.

[39]  Zhenda Lu,et al.  Syntheses, Structures, and Photoluminescent and Magnetic Studies of Metal−Organic Frameworks Assembled with 5-Sulfosalicylic Acid and 1,4-Bis(imidazol-1-ylmethyl)-benzene , 2007 .

[40]  Song Gao,et al.  Two 3D porous lanthanide-fumarate-oxalate frameworks exhibiting framework dynamics and luminescent change upon reversible de- and rehydration. , 2007, Inorganic chemistry.

[41]  G. Qian,et al.  Enhanced near-infrared-luminescence in an erbium tetrafluoroterephthalate framework. , 2006, Inorganic chemistry.

[42]  M. Ward,et al.  Structural and photophysical properties of coordination networks combining [Ru(Bpym)(CN)4]2- or [[Ru(CN)4]2(mu-bpym)]4- anions (bpym = 2,2'-bipyrimidine) with lanthanide(III) cations: sensitized near-infrared luminescence from Yb(III), Nd(III), and Er(III) following Ru-to-lanthanide energy transfer. , 2006, Inorganic chemistry.

[43]  W. Wang,et al.  Luminescent Carbon Nanotubes by Surface Functionalization , 2006, Advanced Materials.

[44]  J. Bünzli.  Benefiting from the unique properties of lanthanide ions. , 2006, Accounts of chemical research.

[45]  C. Sangregorio,et al.  Molecular engineering for single-chain-magnet behavior in a one-dimensional dysprosium-nitronyl nitroxide compound. , 2005, Angewandte Chemie.

[46]  S. Quici,et al.  Visible and near-infrared intense luminescence from water-soluble lanthanide [Tb(III), Eu(III), Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), Er(III)] complexes. , 2005, Inorganic chemistry.

[47]  C. Serre,et al.  Synthesis, characterisation and luminescent properties of a new three-dimensional lanthanide trimesate: M((C6H3)–(CO2)3)(M = Y, Ln) or MIL-78 , 2004 .

[48]  S. Koshihara,et al.  Lanthanide double-decker complexes functioning as magnets at the single-molecular level. , 2003, Journal of the American Chemical Society.

[49]  M. Zaworotko,et al.  Exciplex fluorescence of ([Zn(bipy)1.5(NO3)2)].CH3OH.0.5pyrene)n: a coordination polymer containing intercalated pyrene molecules (bipy = 4,4'-bipyridine). , 2002, Chemical communications.

[50]  M. Ward,et al.  Structural and Photophysical Properties of Mononuclear and Dinuclear Lanthanide(III) Complexes of Multidentate Podand Ligands Based on Poly(pyrazolyl)borates , 1999 .

[51]  A. Caneschi,et al.  Manganese(III) Formate: A Three-Dimensional Framework That Traps Carbon Dioxide Molecules. , 1999, Angewandte Chemie.

[52]  Maria Cristina Burla,et al.  SIR97: a new tool for crystal structure determination and refinement , 1999 .

[53]  Louis J. Farrugia,et al.  ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User Interface (GUI) , 1997 .

[54]  Richard H. Friend,et al.  An improved experimental determination of external photoluminescence quantum efficiency , 1997 .

[55]  Massimo Guardigli,et al.  Luminescent lanthanide complexes as photochemical supramolecular devices , 1993 .

[56]  J. Legendziewicz,et al.  Spectroscopy studies and crystal structure determination of [Ln(HCOO)3 · 2(HCONH2)] crystals , 1986 .

[57]  M. Nardelli,et al.  Parst: A system of fortran routines for calculating molecular structure parameters from results of crystal structure analyses , 1983, Comput. Chem..

[58]  E. Würzberg,et al.  Energy gap law in the solvent isotope effect on radiationless transitions of rare earth ions , 1975 .

[59]  J. Robichaux,et al.  Zero-Field Magnetic Relaxation in Cerous Magnesium Nitrate below 0.2 K , 1971 .

[60]  A. Pabst.  Crystal Structure of Gadolinium Formate, Gd(OOCH)3 , 1943 .