Institute for Soldier Nanotechnologies and Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.
Department of Chemistry, Department of Biological Engineering and Center for Environmental Health Sciences, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
Dalton Trans. 2023 Mar 7;52(10):3219-3233. doi: 10.1039/d2dt03848j.
Cu(I) from tetrakis(acetonitrile)copper(I) hexafluorophosphate ([Cu(MeCN)]PF) was complexed with five structurally related phosphines containing N-heterocycles. The interactions between the resulting complexes and some -nitrosamines were studied using X-ray crystallography as well as emission spectroscopy. Upon complexation, three phosphine ligands bridge two Cu(I) centers to give paddlewheel type structures that displayed a range of emission wavelengths spanning the visible region. -Nitrosodimethylamine (NDMA) was shown to coordinate to one of the two copper centers in some of the paddlewheel complexes in the solid state and this interaction also quenches their emissions in solution. The influence of the weakly coordinating anion on crystal and spectroscopic properties of one of the paddlewheel complexes was also examined using tetrakis(acetonitrile)copper(I) perchlorate ([Cu(MeCN)]ClO) as an alternative Cu(I) source. Similarly, copper(II) perchlorate hexahydrate (Cu(ClO)·6HO) was used for complexation to observe the impact of metal oxidation state on the two aforementioned properties. Lastly, the spectroscopic properties of the complex between PhP(1-Isoquinoline) and Cu(I) was shown to exhibit solvent dependence when the counterion is ClO. These Cu(I) complexes are bench stable solids and may be useful materials for developing a fluorescence based detection method for -nitrosamines.
将四（乙腈）一价铜六氟磷酸盐 ([Cu(MeCN)]PF) 中的 Cu(I) 与五个结构相关的含氮杂环膦配体配位。使用 X 射线晶体学和发射光谱研究了所得配合物与一些亚硝胺之间的相互作用。配位后，三个膦配体桥接两个 Cu(I) 中心，形成了呈现可见区域内一系列发射波长的桨轮型结构。亚硝胺二甲胺 (NDMA) 在固态中被证明与一些桨轮配合物中的一个铜中心配位，这种相互作用也会使它们在溶液中的发射猝灭。还使用四（乙腈）一价高氯酸盐 ([Cu(MeCN)]ClO) 作为替代的 Cu(I) 源，研究了弱配位阴离子对一个桨轮配合物的晶体和光谱性质的影响。同样，使用六水合二价高氯酸铜 (Cu(ClO)·6HO) 进行配位，以观察金属氧化态对上述两种性质的影响。最后，当反离子为 ClO 时，PhP(1-异喹啉) 和 Cu(I) 之间的配合物的光谱性质表现出溶剂依赖性。这些 Cu(I) 配合物是稳定的固体，可用于开发基于荧光的亚硝胺检测方法。
