A. Water Exchange 2326 B. Proton Exchange 2327 C. Electronic Relaxation 2327 D. Relaxivity 2331 E. Outerand Second-Sphere Relaxivity 2334 F. Methods of Improving Relaxivity 2336 V. Macromolecular Conjugates 2336 A. Introduction 2336 B. General Conjugation Methods 2336 C. Synthetic Linear Polymers 2336 D. Synthetic Dendrimer-Based Agents 2338 E. Naturally Occurring Polymers (Proteins, Polysaccharides, and Nucleic Acids) 2339

https://mriquestions.com/uploads/3/4/5/7/34572113/lauffer_1999_review.pdf

Gadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and Applications

Artificial Organic Host Molecules for Anions

3.2. Thienothiophenes 1216 3.2.1. Thieno[3,4-b]thiophene Analogues 1216 3.2.2. Thieno[3,2-b]thiophene Analogues 1217 3.2.3. Thieno[2,3-b]thiophene Analogues 1218 3.3. , ′-Bridged Bithiophenes 1219 3.3.1. Dithienothiophene (DTT) Analogues 1220 3.3.2. Dithieno[3,2-b:2′3′-d]thiophene-4,4-dioxides 1221 3.3.3. Dithienosilole (DTS) Analogues 1221 3.3.4. Cyclopentadithiophene (CPDT) Analogues 1221 3.3.5. Nitrogen and Phosphor Atom Bridged Bithiophenes 1222

Functional oligothiophenes: molecular design for multidimensional nanoarchitectures and their applications.

As a result of the different degrees of stabilization experienced by the 4f, 5d, and 6s orbitals occurring upon ionization of the neutral metal, the lanthanides (La-Lu, Z ) 57-71) exist almost exclusively in their trivalent state Ln(III) ([Xe]4fn, n ) 0-14) in coordination complexes or supramolecular assemblies.1 Except for some arene compounds involving bulky substituted benzenes or cyclo-octatetraenes,2 covalence plays a minor role in Ln-ligand dative bonds and the nature of the coordination sphere is controlled by a subtle interplay between electrostatic interactions and interligand steric constraints.3 Variable coordination numbers (6 e CN e 12) and geometries are thus observed in lanthanide complexes, leading to limited success in the design of molecular architectures with predetermined structures.3,4 Although rigid or semirigid receptors may help to control the coordination sphere according to the lock-and-key and induced fit concepts,5 detailed studies of lanthanide solvates with water or acetonitrile suggest that trivalent lanthanides display a tendency to adopt nine-coordinate tricapped trigonal prismatic (TTP) arrangements around the metal ion in the solid state. In solution, the picture is a little more subtle:6 in water, for instance, large Ln(III) ions at the beginning of the series (Ln ) La-Nd) adopt TTP geometries, which are gradually transformed into eight-coordinate square antiprismatic (SAP) arrangements for small Ln(III) ions (Ln ) Tb-Lu), equilibria between CN ) 8 and CN ) 9 being observed for Ln ) Nd-Tb.7 The systematic contraction of the ionic radii observed when going from Ln ) La to Lu (often referred to as the lanthanide contraction)8 explains this trend and increases electrostatic bonding for heavier lanthanides, but this variation is so smooth and limited (15% contraction between La and Lu and ≈1% between two successive lanthanides) that selective recognition and incorporation into organized supramolecular architectures remains challenging.5 A rational access to extended polymetallic lanthanide-containing assemblies with predictable and controlled geometries is consequently very limited, and pioneer work in this field has focused on poorly characterized intricate mixtures of complexes in solution which are ‘transformed’ into well-defined solid-state clusters or networks through crystallization processes involving a rich palette of † Institute of Molecular and Biological Chemistry, Lausanne. E-mail: Jean-Claude.Bunzli@epfl.ch. ‡ Department of Inorganic, Analytical and Applied Chemistry, Geneva. E-mail: Claude.Piguet@chiam.unige.ch.

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Lanthanide-containing molecular and supramolecular polymetallic functional assemblies.

The challenge of cyclic and acyclic schiff bases and related derivatives

Five-Coordinate Complexes of 21-Thiaporphyrin. Preparations, Spectra, and Structures of Iron(II), Nickel(II), and Copper(II) Complexes.

Rare earth complexes of chiral unsymmetrical hexaazamacrocycles

An esr study on dioxygen adducts of tridentate schiff base cobalt complexes

The condensation of aromatic dialdehydes with chiral diamines, such as 1,2-trans-diaminocyclohexane, leads to various enantiopure or meso-type macrocyclic Schiff bases, including [2 + 2], [3 + 3], [4 + 4], [6 + 6] and [8 + 8] condensation products. Unlike most cases of macrocycle synthesis, the [3 + 3] macrocycles of this type are sometimes obtained in high yields by direct condensation without a metal template. Macrocycles of other sizes from this family can often be selectively obtained in high yields by a suitable choice of metal template, solvent, or chirality of the building blocks. In particular, the application of a cadmium(II) template results in the expansion of the [2 + 2] macrocycles into giant [6 + 6] and [8 + 8] macrocycles. These imine macrocycles can be reduced to the corresponding macrocyclic amines which can act as hosts for the binding of multiple cations or multiple anions.

/pdf/imine-and-amine-type-macrocycles-derived-from-chiral-1t7sxw5c.pdf

Jerzy Lisowski

Papers

Five-Coordinate Complexes of 21-Thiaporphyrin. Preparations, Spectra, and Structures of Iron(II), Nickel(II), and Copper(II) Complexes.

Rare earth complexes of chiral unsymmetrical hexaazamacrocycles

An esr study on dioxygen adducts of tridentate schiff base cobalt complexes

Imine- and Amine-Type Macrocycles Derived from Chiral Diamines and Aromatic Dialdehydes

Tetranuclear Eu(III)-Co(II) complex of an N 4 O 4 macrocycle