Douglas Hagrman

Bio: Douglas Hagrman is an academic researcher from Syracuse University. The author has contributed to research in topics: Coordination complex & Oxide. The author has an hindex of 19, co-authored 28 publications receiving 4901 citations. Previous affiliations of Douglas Hagrman include W. M. Keck Foundation.

Organic-Inorganic Hybrid Materials: From "Simple" Coordination Polymers to Organodiamine-Templated Molybdenum Oxides.

Abstract: A blueprint for the design of oxide materials is provided by nature. By borrowing from nature's 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

Abstract: 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.

Organic/Inorganic Composite Materials: Hydrothermal Syntheses and Structures of the One-, Two-, and Three-Dimensional Copper(II) Sulfate−Organodiamine Phases [Cu(H2O)3(4,4‘-bipyridine)(SO4)]·2H2O, [Cu(bpe)2][Cu(bpe)(H2O)2(SO4)2]·2H2O, and [Cu(bpe)(H2O)(SO4)] (bpe = trans-1,2-Bis(4-pyridyl)ethylene)

Abstract: Three new members of the copper sulfate/heterocyclic diamine family [Cu(4,4‘-bpy)(H2O)3(SO4)]·2H2O (1; 4,4‘-bpy = 4,4‘-bipyridine), [Cu(bpe)2][Cu(bpe)(H2O)2(SO4)2]·2H2O (2; bpe = trans-1,2-bis(4-pyridyl)ethylene), and [Cu(bpe)(H2O)(SO4)] (3) have been synthesized using soft chemical methods. Compound 1 crystallizes as light blue needles from the reaction of a mixture of CuSO4·5H2O, 4,4‘-bipyridine, and H2O in the mole ratio 1:1:2778, that was heated to 200 °C for 24 h. The structure of 1 consists of linear cationic chains of {Cu(4,4‘-bpy)(H2O)3}2+ with SO42- anions as spacers between the chains. Compound 2 crystallizes as dark blue rectangular plates from the reaction of a mixture of CuSO4·5H2O, bpe, and H2O in the mole ratio 1:1:1111, that was initially left to stand at room temperature for 24 h and then heated to 120 °C for an additional 24 h. The structure of 2 exhibits rectangular grids constructed from {Cu(bpe)2}2+ coordination units with linear {Cu(bpe)(H2O)2(SO4)2}2- chains threaded through the gri...

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

Abstract: 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).

Selective gas adsorption and separation in metal–organic frameworks

Abstract: Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate frameworks.

Abstract: Secondary building units (SBUs) are molecular complexes and cluster entities in which ligand coordination modes and metal coordination environments can be utilized in the transformation of these fragments into extended porous networks using polytopic linkers (1,4-benzenedicarboxylate, 1,3,5,7-adamantanetetracarboxylate, etc.). Consideration of the geometric and chemical attributes of the SBUs and linkers leads to prediction of the framework topology, and in turn to the design and synthesis of a new class of porous materials with robust structures and high porosity.

A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands

Abstract: A geometrical analysis has been performed on π–π stacking in metal complexes with aromatic nitrogen-containing ligands based on a Cambridge Structural Database search and on X-ray data of examples in the recent literature. It is evident that a face-to-face π–π alignment where most of the ring-plane area overlaps is a rare phenomenon. The usual π interaction is an offset or slipped stacking, i.e. the rings are parallel displaced. The ring normal and the vector between the ring centroids form an angle of about 20° up to centroid–centroid distances of 3.8 A. Such a parallel-displaced structure also has a contribution from π–σ attraction, the more so with increasing offset. Only a limited number of structures with a near to perfect facial alignment exists. The term π–π stacking is occasionally used even when there is no substantial overlap of the π-ring planes. There is a number of metal–ligand complexes where only the edges of the rings interact in what would be better described a C–H⋯π attraction.

Engineering coordination polymers towards applications

Abstract: The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

Engineering Metal Organic Frameworks for Heterogeneous Catalysis

Abstract: 2.2. MOFs with Metal Active Sites 4614 2.2.1. Early Studies 4614 2.2.2. Hydrogenation Reactions 4618 2.2.3. Oxidation of Organic Substrates 4620 2.2.4. CO Oxidation to CO2 4626 2.2.5. Phototocatalysis by MOFs 4627 2.2.6. Carbonyl Cyanosilylation 4630 2.2.7. Hydrodesulfurization 4631 2.2.8. Other Reactions 4632 2.3. MOFs with Reactive Functional Groups 4634 2.4. MOFs as Host Matrices or Nanometric Reaction Cavities 4636