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A unique four‐coordinate, classical gold(I)‐carbonyl complex with substantial backdonation from gold has been isolated by using a B‐methylated and fluorinated tris(pyridyl)borate chelator. Its lighter silver(I) and copper(I) analogs enabled a study of trends in the coinage‐metal family. The B‐arylated ligand version also afforded a gold–carbon monoxide complex that displays a notably low C−O stretch value, but with trigonal planar geometry at the gold. A computational analysis shows that the Au^I−CO bonds of these tris(pyridyl)borate ligand‐supported molecules consist of electrostatic attraction, OC→Au σ‐donation, and very significant Au→CO π‐back‐bonding components. The latter is responsible for the observed C−O stretching frequencies, which are lower than in free CO.

 

Described herein are the synthesis, structure, and photophysics of the iodo-substituted cyclic trinuclear copper( i ) complex, Cu 3 [4-I-3,5-(CF 3 ) 2 Pz] 3 supported by a highly-fluorinated pyrazolate in comparison with its previously reported 4-Br/4-Cl analogues. The crystal structure is stabilised by multiple supramolecular interactions of Cu 3 ⋯I and hydrogen/halogen bonding. The photophysical properties and supramolecular interactions are investigated experimentally/computationally for all three 4-halo complexes vis-à-vis relativistic effects. 

A useful ligand involving three pyridyl donor arms and fluorocarbon substituents surrounding the coordination pocket has been assembled and utilized in coinage metal chemistry. This tris(pyridyl)borate serves as an excellent ligand support for the stabilization of ethylene complexes of copper, silver and gold. 

The functionalization of polycyclic aromatic hydrocarbons (PAHs) via B←N Lewis pair formation offers an opportunity to judiciously fine‐tune the structural features and optoelectronic properties, to suit the demands of applications in organic electronic devices, bioimaging, and as sensitizers for singlet oxygen generation. We demonstrate that the N‐directed electrophilic borylation of 2,6‐di(pyrid‐2‐yl)anthracene offers access to linearly extended acene derivativesPy‐BR(R=Et, Ph, C₆F₅). In comparison to indeno‐fused 9,10‐diphenylanthracene, the formal “BN for CC” replacement inPy‐BRselectively lowers the LUMO, resulting in a much reduced HOMO–LUMO gap. An even more extended conjugated system with seven six‐membered rings in a row (Qu‐BEt) is obtained by borylation of 2,6‐di(quinolin‐8‐yl)anthracene. FluorinatedPy‐BPfshows particularly advantageous properties, including relatively lower‐lying HOMO and LUMO levels, strong yellow‐green fluorescence, and effective singlet oxygen sensitization, while resisting self‐sensitized conversion to its endoperoxide.

 

The functionalization of polycyclic aromatic hydrocarbons (PAHs) via B←N Lewis pair formation offers an opportunity to judiciously fine‐tune the structural features and optoelectronic properties, to suit the demands of applications in organic electronic devices, bioimaging, and as sensitizers for singlet oxygen generation. We demonstrate that the N‐directed electrophilic borylation of 2,6‐di(pyrid‐2‐yl)anthracene offers access to linearly extended acene derivativesPy‐BR(R=Et, Ph, C₆F₅). In comparison to indeno‐fused 9,10‐diphenylanthracene, the formal “BN for CC” replacement inPy‐BRselectively lowers the LUMO, resulting in a much reduced HOMO–LUMO gap. An even more extended conjugated system with seven six‐membered rings in a row (Qu‐BEt) is obtained by borylation of 2,6‐di(quinolin‐8‐yl)anthracene. FluorinatedPy‐BPfshows particularly advantageous properties, including relatively lower‐lying HOMO and LUMO levels, strong yellow‐green fluorescence, and effective singlet oxygen sensitization, while resisting self‐sensitized conversion to its endoperoxide.