Luminescent Functional Metal–Organic Frameworks

Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination

N-Heterocyclic carbenes have become universal ligands in organometallic and inorganic coordination chemistry. They not only bind to any transition metal, be it in low or high oxidation states, but also to main group elements such as beryllium, sulfur, and iodine. Because of their specific coordination chemistry, N-heterocyclic carbenes both stabilize and activate metal centers in quite different key catalytic steps of organic syntheses, for example, C-H activation, C-C, C-H, C-O, and C-N bond formation. There is now ample evidence that in the new generation of organometallic catalysts the established ligand class of organophosphanes will be supplemented and, in part, replaced by N-heterocyclic carbenes. Over the past few years, this chemistry has been the field of vivid scientific competition, and yielded previously unexpected successes in key areas of homogeneous catalysis. From the work in numerous academic laboratories and in industry, a revolutionary turning point in oraganometallic catalysis is emerging.

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/NHC-%20liganden%20Herrmann.pdf

N-heterocyclic carbenes: a new concept in organometallic catalysis.

Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. This critical review describes the latest developments in (i) the sensitization of near-infrared luminescence, (ii) “soft” luminescent materials (liquid crystals, ionic liquids, ionogels), (iii) electroluminescent materials for organic light emitting diodes, with emphasis on white light generation, and (iv) applications in luminescent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation (500 references).

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Lanthanide luminescence for functional materials and bio-sciences

Lanthanide-based luminescent hybrid materials.

Until recently, the production of gallium arsenide, indium phosphide, and related compound semiconductors has fallen in the domain of the materials scientist and the electrical engineer By clever use of classical chemistry, exemplified by the thermal reaction of Me3Ga and AsH3, it is possible to make semiconductors on a commercial scale However, there are some drawbacks associated with the existing methodology, including the environmental and health hazards of handling pyrophoric and toxic starting materials as well as stoichiometry control problems and undesirable side reactions Can the synthetic inorganic and organometallic chemist play a useful role in this important area by designing and developing new reagents for the production of semiconductor materials? We believe the answer is yes, and in this article we discuss a new approach to the preparation of GaAs and InP thin films based on single-source precursors These compounds feature strong σ-bonding between the group III and V elements, together with substituents that are capable of facile thermal elimination The III/V precursors are more stable toward air and moisture and considerably less toxic than either adducts or mixtures of group III and V compounds

Single‐Source III/V Precursors: A New Approach to Gallium Arsenide and Related Semiconductors

Synthesis and x-ray crystal structures of hexakis(trimethylphosphine)tris-.mu.-methylene-diruthenium(III) and its mono- and dicationic derivatives

The Schiff base complexes [Tb3L4(H2O)2]Cl and [Tb3L3(OAc)2Cl] both have unusual multi-decker architectures formed via intramolecular π−π interactions between phenylene units.

Anion dependent self-assembly of "tetra-decker" and "triple-decker"luminescent Tb(III) salen complexes.

A series of 3d−4f heterobimetallic phenylene-bridged Schiff base complexes of the general formula [Zn(μ-L1)Ln(NO3)3(S)n] [Ln = La (1), Nd (2), Gd (3), Er (4), Yb (5); S = H2O, EtOH; n = 1, 2; H2L1 = N,N‘-bis(3-methoxysalicylidene)phenylene-1,2-diamine] and [Zn(μ-L2)Ln(NO3)3(H2O)n] [Ln = La (6), Nd (7), Gd (8), Er (9), Yb (10); n = 1, 2; H2L2 = N,N‘-bis(3-methoxy-5-p-tolylsalicylidene)phenylene-1,2-diamine] were synthesized and characterized. Complexes 1, 2, 4, and 7 were structurally characterized by X-ray crystallography. At room temperature in CH3CN, both neodymium(III) (2 and 7) and ytterbium(III) (5 and 10) complexes also exhibited, in addition to the ligand-centered emission in the UV−vis region, their lanthanide(III) ion emission in the near-infrared (NIR) region. The photophysical properties of the zinc(II) phenylene-bridged complexes (ZnL1 and ZnL2) were measured and compared with those of the corresponding zinc(II) ethylene-bridged complexes (ZnL3 and ZnL4). Our results revealed that, at 77 K, bo...

Heterobimetallic Zn(II)-Ln(III) phenylene-bridged schiff base complexes, computational studies, and evidence for singlet energy transfer as the main pathway in the sensitization of near-infrared Nd3+ luminescence.

Richard A. Jones

Papers

Single‐Source III/V Precursors: A New Approach to Gallium Arsenide and Related Semiconductors

Synthesis and x-ray crystal structures of hexakis(trimethylphosphine)tris-.mu.-methylene-diruthenium(III) and its mono- and dicationic derivatives

Anion dependent self-assembly of "tetra-decker" and "triple-decker"luminescent Tb(III) salen complexes.

Heterobimetallic Zn(II)-Ln(III) phenylene-bridged schiff base complexes, computational studies, and evidence for singlet energy transfer as the main pathway in the sensitization of near-infrared Nd3+ luminescence.

Design and synthesis of a near infra-red luminescent hexanuclear Zn–Nd prism