19287-90-2

Upstream product

• 16872-09-6 1,2-dicarba-closo-dodecaborane⁽¹²⁾ 
• 1079-66-9 chloro-diphenylphosphine 
• 109-72-8 n-butyllithium 
• 22220-85-5 1,2-dilithio-o-carborane 

Downstream Products

• 12575-35-8 (NiS₂(P(C₆H₅)2)2)(C₂B₁₀H₁₀)2 
• 23868-95-3 1.2-((CO)3Fe(P(C₆H₅)2)2)-1.2-C₂B₁₀H₁₀ 
• 24035-09-4 1.2-(Cl₂Pd(P(C₆H₅)2)2)-1.2-C₂B₁₀H₁₀ 
• 42425-79-6 1.2-((NCS)2Co(P(C₆H₅)2))-1.2-C₂B₁₀H₁₀ 
• 42425-78-5 1.2-(Cl₂Co(P(C₆H₅)2)2)-1.2-C₂B₁₀H₁₀ 
• 19439-53-3 1.2-(Cl₂Ni(P(C₆H₅)2)2)-1.2-C₂B₁₀H₁₀ 
• 19510-53-3 1.2-(I₂Ni(P(C₆H₅)2)2)-1.2-C₂B₁₀H₁₀ 
• 156976-05-5 {Ag(I)(NO₃)(bis(diphanylphosphanyl)-o-carborane)} 
• 142388-92-9 Au₂Cl₂(1,2-bis(diphenylphosphano)-o-carborane) 
• 156976-04-4 {Ag(I)(ClO₄)(bis(diphanylphosphanyl)-o-carborane)} 

Relevant academic research and scientific papers

Thermally Activated Delayed Fluorescence from Ag(I) Complexes: A Route to 100% Quantum Yield at Unprecedentedly Short Decay Time

The four new Ag(I) complexes Ag(phen)(P2-nCB) (1), Ag(idmp)(P2-nCB) (2), Ag(dmp)(P2-nCB) (3), and Ag(dbp)(P2-nCB) (4) with P2-nCB = bis(diphenylphosphine)-nido-carborane, phen = 1,10-phenanthroline, idmp = 4,7-dimethyl-1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, and dbp = 2,9-di-n-butyl-1,10-phenanthroline were designed to demonstrate how to develop Ag(I) complexes that exhibit highly efficient thermally activated delayed fluorescence (TADF). The substituents on the 1,10-phenanthroline ligand affect the photophysical properties strongly (i) electronically via influencing the radiative rate of the S1 → S0 transition and (ii) structurally by rigidifying the molecular geometry with respect to geometry changes occurring in the lowest excited S1 and T1 states. The oscillator strength of the S1 ? S0 transition f(S1 ? S0) - an important parameter for the TADF efficiency being proportional to the radiative rate - can be increased from f(S1 ? S0) = 0.0258 for Ag(phen)(P2-nCB) (1) to f(S1 ? S0) = 0.0536 for Ag(dbp)(P2-nCB) (4), as calculated for the T1 state optimized geometries. This parameter governs the radiative TADF decay time (τr) at ambient temperature, found to be τr = 5.6 μs for Ag(phen)(P2-nCB) (1) but only τr = 1.4 μs for Ag(dbp)(P2-nCB) (4) - a record TADF value. In parallel, the photoluminescence quantum yield (ΦPL) measured for powder samples at ambient temperature is boosted up from ΦPL = 36% for Ag(phen)(P2-nCB) (1) to ΦPL = 100% for Ag(dbp)(P2-nCB) (4). This is a consequence of a cooperative effect of both decreasing the nonradiative decay rate and increasing the radiative decay rate in the series from Ag(phen)(P2-nCB) (1), Ag(idmp)(P2-nCB) (2), and Ag(dmp)(P2-nCB) (3) to Ag(dbp)(P2-nCB) (4). Another parameter important for the TADF behavior is the activation energy of the S1 state from the state T1, ΔE(S1-T1). Experimentally it is determined for the complexes Ag(dmp)(P2-nCB) (3) and Ag(dbp)(P2-nCB) (4) to be of moderate size of ΔE(S1-T1) = 650 cm-1.

Design Strategy for Ag(I)-Based Thermally Activated Delayed Fluorescence Reaching an Efficiency Breakthrough

A design strategy for the development of Ag(I)-based materials for thermally activated delayed fluorescence (TADF) is presented. Although Ag(I) complexes usually do not show TADF, the designed material, Ag(dbp)(P2-nCB) [dbp = 2,9-di-n-butyl-1,10-phenanthroline, and P2-nCB = nido-carborane-bis(diphenylphosphine)], shows a TADF efficiency breakthrough exhibiting an emission decay time of τ(TADF) = 1.4 μs at a quantum yield of ΦPL = 100%. This is a consequence of three optimized parameters. (i) The strongly electron-donating negatively charged P2-nCB ligand destabilizes the 4d orbitals and leads to low-lying charge (CT) states of MLL′CT character, with L and L′ being the two different ligands, thus giving a small energy separation between the lowest singlet S1 and triplet T1 state of ΔE(S1-T1) = 650 cm-1 (80 meV). (ii) The allowedness of the S1 → S0 transition is more than 1 order of magnitude higher than those found for other TADF metal complexes, as shown experimentally and by time-dependent density functional theory calculations. Both parameters favor a short TADF decay time. (iii) The high quantum efficiency is dominantly related to the rigid molecular structure of Ag(dbp)(P2-nCB), resulting from the design strategy of introducing n-butyl substitutions at positions 2 and 9 of phenanthroline that sterically interact with the phenyl groups of the P2-nCB ligand. In particular, the shortest TADF decay time of τ(TADF) = 1.4 μs at a ΦPL value of 100%, reported so far, suggests the use of this outstanding material for organic light-emitting diodes (OLEDs). Importantly, the emission of Ag(dbp)(P2-nCB) is not subject to concentration quenching. Therefore, it may be applied even as a 100% emission layer.

Redox-switchable carboranes for uranium capture and release

The uranyl ion (UO2 2+; U(vi) oxidation state) is the most common form of uranium found in terrestrial and aquatic environments and is a central component in nuclear fuel processing and waste remediation efforts. Uranyl capture from either seawater or nuclear waste has been well studied and typically relies on extremely strong chelating/binding affinities to UO2 2+ using chelating polymers1,2, porous inorganic3–5 or carbon-based6,7 materials, as well as homogeneous8 compounds. By contrast, the controlled release of uranyl after capture is less established and can be difficult, expensive or destructive to the initial material2,9. Here we show how harnessing the redox-switchable chelating and donating properties of an ortho-substituted closo-carborane (1,2-(Ph2PO)2-1,2-C2B10H10) cluster molecule can lead to the controlled chemical or electrochemical capture and release of UO2 2+ in monophasic (organic) or biphasic (organic/aqueous) model solvent systems. This is achieved by taking advantage of the increase in the ligand bite angle when the closo-carborane is reduced to the nido-carborane, resulting in C–C bond rupture and cage opening. The use of electrochemical methods for uranyl capture and release may complement existing sorbent and processing systems.

Direct synthesis of an anionic 13-vertex closo-cobaltacarborane cluster

Reaction of 1,2-bis(diphenylphosphino)-ortho-carborane (L) with [K(thf){(MesBIAN)Co(η4-cod)}] (1, MesBIAN = bis(mesityliminoace-naphthene)diimine, cod = 1,5-cyclooctadiene) affords an anionic 13-vertex closo-cobaltacarborane cluster (2) in one step. The mechanism of this transformation has been studied by experimental and quantum chemical techniques, which suggest that a series of outer-sphere electron transfer and isomerisation processes occurs. This work shows that low-valent metalate anions are promising reagents for the synthesis of anionic metallacarborane clusters.

Efficient Color-Tunable Copper(I) Complexes and Their Applications in Solution-Processed Organic Light-Emitting Diodes

A series of dppnc- and neocuproine-based CuI complexes (dppnc=7,8-bis(diphenylphosphino)-7,8-dicarba-nido-undecaborate) are synthesized and the emission color of these CuI complexes can be tuned from green to deep red via rational modification of the neocuproine ligand structure. The molecular structures of the emissive CuI complexes, Cu(dppnc)-G (green emitting), Cu(dppnc)-Y (yellow emitting), and Cu(dppnc)-R (red emitting), are characterized and their electronic structures and related transition properties are elucidated by photo-physical and computational (density functional theory) studies. The calculation results suggest that thermally activated delayed fluorescence (TADF) is the emission mechanism for these CuI complexes. Efficient solution-processed green-, yellow-, and red-emitting OLEDs are fabricated based on the emissive complexes as the dopants. High external quantum efficiency (EQE) of 15.20 % and current efficiency of 48.15 cd A?1 at 1000 cd m?2 are achieved in the green-emitting device with Cu(dppnc)-G. A maximum EQE of 10.17 %, CIE coordinates of (0.61, 0.38) and a maximum electroluminescent peak of 631 nm are achieved in the red device based on Cu(dppnc)-R.

Ionic composite of palladium(II)/iron bis(dicarbollide) for catalytic oxidative carbonylation in the formation of diphenyl carbonate

The carborane-based sandwich iron complex, [n-Bu4N]{Fe(3,3′)-[1,2-(PPh2)2-1,2-C2B9H9]2}, was synthesized in 53.1% yield. A catalyst composite of PdAc2/[n-Bu4N]{Fe(3,3′)-[1,2-(PPh2)2-1,2-C2B9H9]2} was found to be highly active for the oxidative carbonylation of phenol, with the formation of diphenyl carbonate (DPC). A DPC yield of 46% and a turnover number (TON) of 511 were achieved in 4 h using the composite at 110 °C. For comparison, the reaction was also investigated using catalyst composites of PdAc2/Mn(acac)3, PdAc2/Fe(acac)3, PdAc2/Co(acac)3 and PdAc2/Ce(acac)3 (acac = acetylacetone) under the same conditions of temperature and pressure. The DPC yield was determined by gas chromatography with flame ionization detector (GC-FID). All new products were characterized by elemental analysis, and by 1H, 13C, 11B and 31P NMR and FT-IR spectroscopy.

Long-lived excited states of zwitterionic copper(I) complexes for photoinduced cross-dehydrogenative coupling reactions

Four heteroleptic copper(I) complexes containing phenanthroline and monoanionic nido-carborane-diphosphine ligands have been prepared and structurally characterized by various spectroscopic techniques and X-ray diffraction. These complexes exhibit intense

Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity

The neutral Cp*M(Cl)(1-PPh2-2-S-1,2-C2B 10H10) and zwitterionic Cp*M(3-OCH 3-7-PPh2-8-S-7,8-C2B9H9) (Cp* = η5-C5Me5, M = Ir, Rh, 1-PPh2-2-S-1,2-C2B10H10 = [1-(diphenylphosphino)-2-thiolato)-1,2-dicarba-closo-carborane], 3-OCH 3-7-PPh2-8-S-7,8-C2B9H9 = [3-(methoxyl)-7-(diphenylphosphino)-8-(thiolato)-7,8-dicarba-nido-carborane] -) were synthesized and fully characterized. The 18-electron neutral closo-carborane complexes Cp*M(Cl)(1-PPh2-2-S-1,2-C 2B10H10) (M = Ir (1a), Rh (1b)) can be easily deboronated to result in the formation of reactive 16-electron zwitterionic nido-carborane complexes [Cp*M(3-OCH3-7-PPh2-8-S-7, 8-C2B9H9)] (M = Ir (2a), Rh(2b)). The oxidation of 2b with O2 gas afforded the corresponding sulfone complex 3b in high yields. Utilization of its unsaturated feature in 16-electron zwitterionic nido-carborane complexes offers a potential strategy to synthesize new types of organometallic complexes.

CARBORANE-PHOSPHONIUM COMPOUNDS AND THEIR USE IN BORON NEUTRON CAPTURE THERAPY AND IMAGING

The invention describes compounds for use in BCNT. These compounds comprise a carborane group coupled to a phosphorus containing group. The compounds may comprise a carborane group coupled to a phosphonium group.