Photoluminescent nickel(Ⅱ)carbene complexes with ligand-to-ligand charge-transfer excited states

While nickel(II)complexes have been widely used as catalysts for carbon-carbon coupling reactions,the exploration of their photophysical and photochemical properties is still in the infancy.Here,a series of square-planar Ni(II)complexes[(diNHC)NiX2]bearing chelating benzimidazole-based bis(N-heterocyclic carbene)ligands and varying anionic coligands(1,X=Cl;2,X=Br;3,X=I)are synthesized and structurally characterized.In solid state,both 1 and 2 exhibit orange-red photoluminescence under ambient conditions.The photophysical and electrochemical measurements along with density functional theory(DFT)calculations reveal that the low-energy emissions can be attributed to singlet excited states with ligand-to-ligand charge-transfer(LLCT)character.This work suggests that strong-field N-heterocyclic carbene ligands play a crucial role to achieve the luminescence of Ni(II)complexes.

Ratiometric hypoxia detection by bright organic room temperature phosphorescence of uniformed silica nanoparticles in water

Organic room temperature phosphorescence(RTP)in water has attracted much attention recently for its potential biological applications.However,it remains a formidable challenge to achieve efficient RTP from pure organic compounds in aqueous phase due to the dramatic deactivation of triplet excited states in water and the poor water dispersibility of large organic particles/crystals.Represented herein is covalent incorporation of a pure organic monochromophore in silica nanoparticles(SiNPs)featuring fluorescence and bright phosphorescence in aqueous solution.The covalent bonding of organic phosphors in polysiloxane framework was found to show excellent water dispersibility,at the same time suppress the nonradiative deactivation of triplet excited states especially from water,thus leading to high phosphorescence quantum yields(up to 22%)and long lifetimes(up to 3.5 ms)in aqueous phase.More strikingly,oxygen-insensitive fluorescence as internal reference and oxygen-dependent phosphorescence as oxygen indicator from the organic chromophore in the porous SiNPs realized ratiometric hypoxia detection with ultrasensitivity(K_(SV)=449.3 bar^(-1)).

通过P–H键对磷烯进行表面功能化以提升磷烯的稳定性并实现高效光催化产H_(2)

在大气环境下,寡层黑磷(简称为磷烯)很容易被氧化,因此阻碍了其在光催化太阳能转换领域的应用.相关的一些保护方法,比如在磷烯表面引入保护层、表面配位、P–C共价官能化等方法可以维持磷烯的稳定性,使其免受氧化降解,可是这些方法对磷烯的催化活性位点造成了堵塞,因此不可避免地降低了其光催化活性.在本项工作中,我们开发了一种在磷烯表面引入P–H共价键的策略,表面P–H共价键的引入既能维持磷烯在大气环境下的稳定性,又能实现高效光催化分解水产H_(2).相关实验和DFT计算表明,磷烯表面约5 mol%的磷原子参与了P–H共价键的形成,在热力学和动力学两方面同时抑制了磷烯的氧化反应.磷烯的表面氢化策略有希望促进磷烯在光催化领域的实际应用.