Jon Zubieta

Organic-inorganic hybrid materials: From 'simple' coordination polymers to organodiamine-templated molybdenum oxides

A blueprint for the design of oxide materials is provided by nature. By borrowing from natures ability to influence inorganic microstructures in biomineralization processes and in the hydrothermal synthesis of complex minerals, a new class of materials in which organic components exert a role in controlling inorganic microstructure is evolving. By employing members of the ever-expanding class of polymeric coordination complex cations, novel molybdenum oxide substructures, such as the one shown, may be prepared.

Solid-State Coordination Chemistry: The Self-Assembly of Microporous Organic–Inorganic Hybrid Frameworks Constructed from Tetrapyridylporphyrin and Bimetallic Oxide Chains or Oxide Clusters

The hydrothermal reactions of MoO(3), tetrapyridylporphyrin (tpypor), water, and the appropriate M(II) precursor yield the first examples of three-dimensional framework materials constructed from metal oxide and porphyrin subunits. The picture shows a section of [{Fe(tpypor)}(3)Fe(Mo(6)O(19))(2)] small middle dotx H(2)O with the [Fe(8)(tpypor)(6)](8+) building block of the cationic framework and the entrained {Mo(6)O(19)}(2-) cluster.

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]·4H2O

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]�4H2O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P5+. These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH3)2NH2+ and K+ cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P43 with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.

Technetium and Gallium Derived Radiopharmaceuticals: Comparing and Contrasting the Chemistry of Two Important Radiometals for the Molecular Imaging Era

ment of therapies, allows for selection of the most potent interventions, and is a way to assess early on during therapy * Corresponding authors: (J.F.V.) E-mail: valliant@mcmaster.ca. Fax: 905522-7776. Tel.: 905-525-9140 ext. 22840. (J.Z.) E-mail: jazubiet@syr.edu. Fax: 315-443-4070. Tel.: 315-443-2547. † Syracuse University. ‡ McMaster University. § Current address: Children’s Hospital Boston, Division of Nuclear Medicine, Department of Radiology, 300 Longwood Avenue, Boston, MA 02115. Mark Daniel Bartholomä was born in Neunkirchen (Germany) and received his diploma (2002) and his doctoral degree (2007) from the Saarland University in Saarbrücken (Germany) under the supervision of Prof. Kaspar Hegetschweiler on the synthesis and complex formation of multidentate derivatives of 1,3,5-triamino-1,3,5-trideoxy-cis-inositol. After a postdoctoral appointment in Prof. Jon Zubieta’s research group at Syracuse University working on Re/Tc conjugated nucleoside analogues for noninvasive imaging from 2007 to 2009, he joined Prof. Alan Packard’s group in 2010 at Harvard Medical School to study 18F radiolabeled perfusion tracers. Educated as a coordination chemist, his research interests focus on the development of novel ligand systems and investigation of their corresponding complex formation as well as their biochemical background and medical applications including the development of radiopharmaceuticals.

Organisch-anorganische Hybridmaterialien: von „einfachen” Koordinationspolymeren zu Molybdänoxiden mit Organodiamin-Templaten

Eine Blaupause fur das Design von Oxidmaterialien kann uns die Natur liefern, da sie bei Biomineralisationsprozessen und bei der Hydrothermalsynthese komplexer Mineralien anorganische Mikrostrukturen beeinflussen kann. Eine Anleihe bei dieser Fahigkeit fuhrt zu einer ganz neuen Klasse von Materialien, bei denen organische Komponenten eine Rolle bei der Kontrolle uber die anorganischen Mikrostrukturen spielen. Der Einsatz von Verbindungen aus der bestandig wachsenden Klasse polymerer Komplexkationen ermoglicht die Herstellung von Molybdanoxiden mit neuartigen Substrukturen (siehe das im Bild gezeigte Beispiel).

New solids from old clusters: syntheses and structures of [Cu(en)2]2[Mo8O26], [Cu(enMe)2]3[V15O36Cl]·2.5H2O and Cs0.5[Ni(en)2]3[V18O42Cl]·2en·6H2O

Abstract One-dimensional and two-dimensional solids consisting of polyoxoanions bridged by (M(LL)2)2+ groups have been synthesized by hydrothermal methods and structurally characterized by X-ray crystallography.

Molecular manipulation of solid state structure: Influences of organic components on vanadium oxide architectures

Abstract Among the inorganic materials enjoying widespread contemporary interest, the metal oxide based solid phases occupy a prominent position by virtue of their applications to catalysis, sorption, molecular electronics, energy storage, optical materials and ceramics. The diversity of properties associated with these materials reflects the chemical composition, which allows variations in covalency, geometry and oxidation states, and the crystalline architecture, which may provide different pore structures, coordination sites, or juxtapositions of functional groups. Despite such fundamental and practical significance, the design of the structure of such materials remains a challenge in solid state chemistry. While organic materials have been synthesized which self-assemble into ordered arrays at low temperature and which exhibit molecular recognition and biomimetic activity, the ability to synthesize inorganic materials by rational design remains elusive. Small, soluble molecular building blocks with well-defined reaction chemistries which allow their low-temperature assembly into crystalline solid state inorganic materials are not well known. However, the existence of naturally occurring, structurally complex minerals establishes that hydrothermal synthesis can provide a low temperature pathway to produce open-framework and layered metastable structures utilizing inorganic starting materials. Thus, hydrothermal conditions have been used to prepare microporous tetrahedral framework solids that are capable of shape-selective absorption, like zeolites and aluminophosphates, and more recently in the preparation of complex solid arrays of the M/O/PO3−4 and M/O/RPO2−3 systems (M=V and Mo). The hydrothermal technique may be combined with the introduction of organic components which may act as charge compensating groups, space-filling units, structure directing agents, templates, tethers between functional groups, or conventional ligands in the preparation of inorganic/organic composites. In the past decade, this general strategy has been exploited in the evolution of a family of vanadium oxides incorporating structure-directing organic or secondary-metal organic subunits, which are the topic of this review. The synthetic approach to novel vanadium oxide solids occupies the interface between materials science and coordination chemistry. The emerging theme focuses on the association of an organic component, acting as a ligand, tether, or structure directing moiety, with the inorganic framework of the solid to provide unique composites. While some organic components may limit the size of inorganic cluster subunits of a solid by passivating the surface of an aggregate through capping, such ligands may also serve to link inorganic subunits into complex networks. In other cases, the organic subunit, rather than participating as a covalently bound unit of the framework, acts in a structure directing role, producing amphiphilic materials whose structures are determined by hydrophobic–hydrophilic interactions. This latter feature is reminiscent of the factors influencing biomineralization, a field which may prove relevant to the development of new strategies for the controlled synthesis of organized inorganic and organic/inorganic composite materials. These various approaches to the “design” of inorganic solids are discussed and assessed in terms of the new structural types recently observed in the vanadium oxide chemistry.

A Thermally and Hydrolytically Stable Microporous Framework Exhibiting Single‐Chain Magnetism: Structure and Properties of [Co2(H0.67bdt)3]⋅20 H2O

Fixing a hole: Hydrothermal chemistry has been exploited in the preparation of a 3D framework material exhibiting 48% accessible void volume and 1.5% hydrogen uptake by weight at 120 kPa (see picture). The title compound also exhibits single-chain magnetic behavior and reversible changes in magnetic properties upon solvation and desolvation.

Organic/inorganic composite materials: the roles of organoamine ligands in the design of inorganic solids

Abstract The influence of organic components on the microstructure of inorganic solids has been extensively documented in recent years and has been shown to provide an efficacious method for the design of new materials. The synergism between the various chemical constituents at the organic/inorganic interface may result in imprinting of structural information from the organic molecules onto the inorganic framework. In this paper, the structural consequences of introducing organic components into several families of materials, including oxometalphosphates, transition metal oxides and transition metal halides and pseudohalides are briefly reviewed.

Solid state coordination chemistry of metal-1,2,4-triazolates and the related metal-4-pyridyltetrazolates

This short review focuses on the structural chemistry of the coordination polymers of 1,2,4-triazole (Htrz) and the 1,2,4-triazolate ligand (trz) and of 4-pyridyltetrazolate (pt) which can be considered as an expanded analogue of 1,2,4-triazolate. The structures are discussed in terms of some common building blocks and the sorptive and magnetic properties of these materials.