Anion-directed self-assembly of lanthanide-notp compounds and their fluorescence, magnetic, and catalytic properties.

Reactions of 1,4,7-triazacyclononane-1,4,7-triyl-tris(methylenephosphonic acid) [notpH(6), C(9)H(18)N(3)(PO(3)H(2))3] with different lanthanide salts result in four types of Ln-notp compounds: [Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(NO(3))(H(2)O)].4H2O (1), [Ln = Eu (1 Eu), Gd (1 Gd), Tb (1 Tb)], [Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]Cl.3H2O (2) [Ln = Eu (2 Eu), Gd (2 Gd), Tb (2 Tb)], [Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]ClO4.8H2O, (3) [Ln = Eu (3 Eu), Gd (3 Gd)], and [Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]ClO4.3H2O (4), [Ln = Gd (4 Gd), Tb (4 Tb)]. Compounds within each type are isostructural. In compounds 1, dimers of {Ln2(notpH4)2(NO3)2(H2O)2} are found, in which the two lanthanide atoms are connected by two pairs of O-P-O and one pair of mu-O bridges. The NO3- ion serves as a bidentate terminal ligand. Compounds 2 contain similar dimeric units of {Ln2(notpH4)2(H2O)2} that are further connected by a pair of O-P-O bridges into an alternating chain. The Cl- ions are involved in the interchain hydrogen-bonding networks. A similar chain structure is also found in compounds 3; in this case, however, the chains are linked by ClO4- counterions through hydrogen-bonding interactions, forming an undulating layer in the (011) plane. These layers are fused through hydrogen-bonding interactions, leading to a three-dimensional supramolecular network with large channels in the [100] direction. Compounds 4 show an interesting brick-wall-like layer structure in which the neighboring lanthanide atoms are connected by a pair of O-P-O bridges. The ClO4- counterions and the lattice water molecules are between the layers. In all compounds the triazamacrocyclic nitrogen atoms are not coordinated to the Ln(III) ions. The anions and the pH are believed to play key roles in directing the formation of a particular structure. The fluorescence spectroscopic properties of the Eu and Tb compounds, magnetic properties of the Gd compounds, and the catalytic properties of 4 Gd were also studied.

[1]  J. Tallarico,et al.  Demonstration of the feasibility of a direct solid-phase split-pool Biginelli synthesis of 3,4-dihydropyrimidinones. , 2004, Organic letters.

[2]  Weisheng Liu,et al.  Lanthanide coordination polymers and their Ag+-modulated fluorescence. , 2004, Journal of the American Chemical Society.

[3]  Bin Zhao,et al.  Coordination polymers containing 1D channels as selective luminescent probes. , 2004, Journal of the American Chemical Society.

[4]  Li‐Min Zheng,et al.  Incorporation of triazacyclononane into the metal phosphonate backbones. , 2006, Inorganic chemistry.

[5]  C. Kappe.  Recent advances in the Biginelli dihydropyrimidine synthesis. New tricks from an old dog. , 2000, Accounts of chemical research.

[6]  A. Sherry,et al.  Towards the rational design of magnetic resonance imaging contrast agents: isolation of the two coordination isomers of lanthanide DOTA-type complexes. , 2003, Angewandte Chemie.

[7]  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 .

[8]  S. Haggarty,et al.  Small molecule inhibitor of mitotic spindle bipolarity identified in a phenotype-based screen. , 1999, Science.

[9]  V. Jacques,et al.  Auto-assembling of ditopic macrocyclic lanthanide chelates with transition-metal ions. Rigid multimetallic high relaxivity contrast agents for magnetic resonance imaging. , 2006, Inorganic chemistry.

[10]  R. Ziessel,et al.  Lanthanide probes for luminescence microscopy and anion sensing , 2004 .

[11]  J. Mosinger,et al.  Synthesis, crystal structures and NMR and luminescence spectra of lanthanide complexes of 1,4,7,10-tetraazacyclododecane with N-methylene(phenyl)phosphinic acid pendant arms† , 1999 .

[12]  YooJin Kim,et al.  Crystal structure and spectroscopic study of novel two- and three-dimensional photoluminescent Eu(III)-adipate compounds. , 2004, Inorganic chemistry.

[13]  C. Kappe.  Biologically active dihydropyrimidones of the Biginelli-type--a literature survey. , 2000, European journal of medicinal chemistry.

[14]  Eliana Gianolio,et al.  [Gd-AAZTA]-: a new structural entry for an improved generation of MRI contrast agents. , 2004, Inorganic chemistry.

[15]  M. Botta,et al.  Gadolinium(III) Complexes of dota‐Derived N‐Sulfonylacetamides (H4(dota‐NHSO2R)=10‐{2‐[(R)sulfonylamino]‐2‐oxoethyl}‐1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic Acid): A New Class of Relaxation Agents for Magnetic Resonance Imaging Applications , 2005 .

[16]  M. Welch,et al.  A novel hexachelating amino-thiol ligand and its complex with gallium(III) , 1990 .

[17]  J. P. Cox,et al.  Structure and Solution Stability of Indium and Gallium Complexes of 1, 4,7‐Triazacyclononanetriacetate and of Yttrium Complexes of 1,4,7,10‐ Tetraazacyclododecanetetraacetate and Related Ligands: Kinetically Stable Complexes for Use i , 1991 .

[18]  C. Lodeiro,et al.  Metal complexes with a new N(4)O(3) amine pendant-armed macrocyclic ligand: synthesis, characterization, crystal structures, and fluorescence studies. , 2003, Inorganic chemistry.

[19]  H. Adams,et al.  Stability, 71Ga NMR, and crystal structure of a neutral gallium(III) complex of 1,4,7-triazacyclononanetriacetate: a potential radiopharmaceutical? , 1989 .

[20]  S. Hatscher,et al.  Crystal structure and magnetic behaviour of a new lanthanide acetate Gd(HF2CCOO)3(H2O)2·H2O in comparison to Gd(H3CCOO)3(H2O)2·2H2O , 2004 .

[21]  A Hedberg,et al.  Dihydropyrimidine calcium channel blockers. 3. 3-Carbamoyl-4-aryl-1,2,3,4-tetrahydro-6-methyl-5-pyrimidinecarboxylic acid esters as orally effective antihypertensive agents. , 1991, Journal of medicinal chemistry.

[22]  C. Malloy,et al.  A new class of macrocyclic lanthanide complexes for cell labeling and magnetic resonance imaging applications. , 2005, Journal of the American Chemical Society.

[23]  K. Wieghardt,et al.  Neue μ‐Hydroxo‐Übergangsmetallkomplexe, I. Darstellung und Struktur des trans‐Diaqua‐di‐μ‐hydroxo‐bis[(1,4,7‐triazacyclononan)cobalt(III)]‐Kations; Kinetik und Mechanismus seiner Bildung , 1979 .

[24]  T. Gunnlaugsson,et al.  Cyclen based lanthanide ion ribonuclease mimics: the effect of pyridine cofactors upon phosphodiester HPNP hydrolysis , 2005 .

[25]  S. H. Koenig,et al.  Evaluation of polyaza macrocyclic methylene phosphonate chelates of Gd3+ ions as MRI contrast agents , 1989, Magnetic resonance in medicine.

[26]  V. Jacques,et al.  Designing new MRI contrast agents: a coordination chemistry challenge , 1999 .

[27]  H. C. Aspinall.  Chiral lanthanide complexes: coordination chemistry and applications. , 2002, Chemical reviews.

[28]  M. Aguirre,et al.  Complexes of macrocycles with pendant arms as models for biological molecules , 2000 .

[29]  A. Jyo,et al.  Crystal Structure of Gallium(III) Complex of 1,4,7-Triazacyclononane-N,N′, N″-triacetate , 1990 .

[30]  Yijun Huang,et al.  Highly enantioselective Biginelli reaction using a new chiral ytterbium catalyst: asymmetric synthesis of dihydropyrimidines. , 2006, Journal of the American Chemical Society.

[31]  C. Qian,et al.  Lanthanide triflate catalyzed Biginelli reaction. one-pot synthesis of dihydropyrimidinones under solvent-free conditions. , 2000, The Journal of organic chemistry.

[32]  A. Sherry,et al.  Synthesis and characterization of 1,4,7-triazacyclononane derivatives with methylphosphinate and acetate side chains for monitoring free MgII by31P and1H NMR spectroscopy , 1996 .

[33]  Thorfinnur Gunnlaugsson,et al.  Towards the development of Eu(III) luminescent switching/sensing in water permeable hydrogels , 2004 .

[34]  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.

[35]  C. Kappe.  The Generation of Dihydropyrimidine Libraries Utilizing Biginelli Multicomponent Chemistry , 2003 .

[36]  R. Dickins,et al.  Asymmetric catalysis by chiral lanthanide complexes in water. , 2005, Chirality.

[37]  L. Overman,et al.  The tethered Biginelli condensation in natural product synthesis. , 2004, Chemical communications.

[38]  R. Lauffer,et al.  Gadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and Applications. , 1999, Chemical reviews.