Tuning main group redox chemistry through steric loading: subvalent Group 13 metal complexes of carbazolyl ligands

The ability of substituted carbazol‐9‐yl systems to ligate in σ fashion through the amido N‐donor, or to adopt alternative coordination modes through the π system of the central five‐membered ring, can be tuned by systematic variation in the steric demands of substituents in the 1‐ and 8‐positions. The differing affinities of the two modes of coordination for hard and soft metal centres can be shown to influence not only cation selectivity, but also the redox properties of the metal centre. Thus, the highly sterically sterically demanding 1,3,6,8‐tetra‐tert‐butylcarbazolyl ligand can be used to generate the structurally characterised amido‐indium(I) complex, [{(tBu₄carb)In}_n], (together with its isostructural thallium counterpart) in which the metal centre interacts with the central pyrrolyl ring in η³ fashion [d(In? N)=2.679(3) Å; d(In? C)=2.819(3), 2.899(3) Å]. By contrast, the smaller 3,6‐di‐tert‐butylcarbazolyl system is less able to restrict the metal centre from binding at the anionic nitrogen donor in the plane of the carbazolyl ligand (i.e. in σ fashion). Analogous chemistry with In^I precursors therefore leads to disproportionation to the much harder In^II [and In⁰], and the formation of the mixed‐valence product, [In₂{In₂(tBu₂carb)₆}], a homoleptic molecular [In₄(NR₂)₆] system. This chemistry reveals a flexibility of ligation for carbazolyl systems that contrasts markedly with that of the similarly sterically encumbered terphenyl ligand family.     

荧光寿命的快速傅里叶变换拟合方法

介绍了一种利用快速傅里叶变换算法对稀土掺杂物质的荧光寿命进行数据拟合的方法。稀土掺杂物质可用来制备多种光学传感器,用于温度、pH值等多种参量测量领域。本方法利用快速傅里叶变换(FFT)结果作为基础,从非零项的相位角的正切值得出被测的荧光寿命,具有速度快、误差小、不受本底干扰等一系列优点。以掺铒光纤为例,通过数字仿真将本方法与其它几种传统的拟合方法进行了比较。快速傅里叶变换方法的测量偏差不到Prony方法的50％,为对数似合(log-fit)方法测量偏差的1／6。另外,快速傅里叶变换方法由于不受本底噪声影响,可以不必在信号处理时去掉本底噪声,因而可以明显缩短测量时间。