Stable and Storable N(CF ) Transfer Reagents.

Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl)amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF ) group are rare.

Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination.

Different types of high-yield, easily scalable syntheses for cyano(fluoro)borates Kt[BF (CN) ] (n=0-2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal-free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates.

Carba-closo-dodecaboranylethynyl ligands facilitating luminescent reversed charge-transfer excited states in gold/silver complexes.

A set of mono- and dinuclear Au and Ag alkynyl complexes bearing the carba-closo-dodecaboranylethynyl ligand show intense room temperature phosphorescence. The {closo-1-CB} cage participates in an unprecedented way as an electron donating moiety, changing the direction of the charge-transfer excited state.

Silver(I) Clusters with Carba-closo-dodecaboranylethynyl Ligands: Synthesis, Structure, and Phosphorescence.

Salts of anionic silver(I) clusters with the carba-closo-dodecaboranylethynyl ligand were obtained from {Ag (12-C≡C-closo-1-CB H )} , selected pyridines, and [Et N]Cl or [Ph P]Br. Salts of octahedral silver(I) clusters [Et N] [Ag (12-C≡C-closo-1-CB H ) (4-X-C H N) ] were formed with pyridine (X=H, x=8), 4-methylpyridine (X=Me, x=8), and 4-cyanopyridine (X=CN, x=10). In contrast, 3,5-lutidine (3,5-Me Py) did not result in salts of dianionic clusters, even in the presence of excess of [Et N]Cl or [Ph P]Br; instead salts of monoanionic Ag clusters, [Et N][Ag (12-C≡C-closo-1-CB H ) (3,5-Me Py) ] and [Ph P][Ag (12-C≡C-closo-1-CB H ) (3,5-Me Py) ] were obtained.

Unprecedented Efficient Structure Controlled Phosphorescence of Silver(I) Clusters Stabilized by Carba-closo-dodecaboranylethynyl Ligands.

{Ag2 (12-C≡C-closo-1-CB11 H11 )}n and selected pyridine ligands have been used for the synthesis of photostable Ag(I) clusters that, with one exception, exhibit for Ag(I) compounds unusual room-temperature phosphorescence. Extraordinarily intense phosphorescence was observed for a distorted pentagonal bipyramidal Ag(I) 7 cluster that shows an unprecedented quantum yield of Φ=0.76 for Ag(I) clusters.

The hexacyanodiborane(6) dianion [B2(CN)6](2-).

Diborane(6) dianions with substituents that are bonded to boron via carbon are very reactive and therefore only a few examples are known. Diborane(6) derivatives are the simplest catenated boron compounds with an electron-precise B-B σ-bond that are of fundamental interest and of relevance for material applications. The homoleptic hexacyanodiborane(6) dianion [B2 (CN)6 ](2-) that is chemically very robust is reported.

Polyfluorinated carba-closo-dodecaboranes with amino and ammonio substituents bonded to boron.

The inner salts x-H3N-closo-1-CB11H11 (x = 12, 2) and 7-H3N-12-F-closo-1-CB11H11 were fluorinated with elemental fluorine in anhydrous hydrogen fluoride to give the B-perfluorinated ammonio derivatives 1-H-x-H3N-closo-1-CB11F10 (x = 12, 7, 2). Deprotonation of the ammonio group yielded the corresponding amino-functionalized anions [1-H-x-H2N-closo-1-CB11F10](-) (x = 12, 7, 2) that were isolated as [Et4N](+) salts. Hydrolysis of the highly fluorinated inner salts 1-H-x-H3N-closo-1-CB11F10 (x = 12, 7, 2) is very slow in acidic aqueous solutions.

Carba-closo-dodecaborate anions with two functional groups: [1-R-12-HC≡C-closo-1-CB₁₁H₁₀]⁻ (R = CN, NC, CO₂H, C(O)NH₂, NHC(O)H).

Disubstituted carba-closo-dodecaborate anions with one functional group bonded to the cluster carbon atom and one ethynyl group bonded to the antipodal boron atom were synthesized from easily accessible {closo-1-CB11} clusters. [Et4N][1-NC-12-HC≡C-closo-1-CB11H10] ([Et4N]4b) was prepared starting from Cs[12-Et3SiC≡C-closo-1-CB11H11] (Cs1c) via salts of the anions [1-HO(O)C-12-HC≡C-closo-1-CB11H10](-) (2b) and [1-H2N(O)C-12-HC≡C-closo-1-CB11H10](-) (3b). In a similar reaction sequence [Et4N][1-CN-12-HC≡C-closo-1-CB11H10] ([Et4N]7b) was obtained from Cs[1-H2N-12-HC≡C-closo-1-CB11H10] (Cs5b) by formamidation to yield [Et4N][1-H(O)CHN-12-HC≡C-closo-1-CB11H10] ([Et4N]6b) and successive dehydration.

Difunctionalized {closo-1-CB11 } clusters: 1- and 2-amino-12-ethynylcarba-closo-dodecaborates.

Carba-closo-dodecaborate anions with two functional groups have been synthesized via a simple two-step procedure starting from monoamino-functionalized {closo-1-CB11 } clusters. Iodination at the antipodal boron atom provided access to [1-H2 N-12-I-closo-1-CB11 H10 ](-) (1 a) and [2-H2 N-12-I-closo-1-CB11 H10 ](-) (2 a), which have been transformed into the anions [1-H2 N-12-RCC-closo-1-CB11 H10 ](-) (R=H (1 b), Ph (1 c), Et3 Si (1 d)) and [2-H2 N-12-RCC-closo-1-CB11 H10 ](-) (R=H (2 b), Ph (2 c), Et3 Si (2 d)) by microwave-assisted Kumada-type cross-coupling reactions. The syntheses of the inner salts 1-Me3 N-12-RCC-closo-1-CB11 H10 (R=H (1 e), Et3 Si (1 f)) and 2-Me3 N-12-RCC-closo-1-CB11 H10 (R=H (2 e), Et3 Si (2 f)) are the first examples for a further derivatization of the new anions.

Metal-organic framework luminescence in the yellow gap by codoping of the homoleptic imidazolate ∞(3)[Ba(Im)2] with divalent europium.

The rare case of a metal-triggered broad-band yellow emitter among inorganic-organic hybrid materials was achieved by in situ codoping of the novel imidazolate metal-organic framework ∞(3)[Ba(Im)2] with divalent europium. The emission maximum of this dense framework is in the center of the yellow gap of primary light-emitting diode phosphors. Up to 20% Eu2+ can be added to replace Ba2+ as connectivity centers without causing observable phase segregation.