Mercury(II) Complexes with Thiacrowns and Related Macrocyclic Ligands

Relativistically corrected electric field gradients calculated with the normalized elimination of the small component formalism

“…14. These calculations are carried out with the use of a very large uncontracted basis set of quadruple-zeta (QZ) qual- 40 and HgCl 2 -crown-S 6 ((Z,Z,Z,Z,Z,Z)-1,4,7,10,13,16-hexathiacyclooctadeca-2,5, 8,11,14,17-hexaene, 41,42 see Figure 1) were optimized using the NESC/B3LYP method. In the geometry optimizations, the segmented all-electron relativistically contracted (SARC) basis set 43 was used for mercury combined with the 6-31+G(d) basis set 44 for other elements.…”

Formation of Organometallic Species, [M – H]+ Ions and Radical Cations upon Mass Spectrometric Fragmentation of Mercury–Crown Ether Complexes

“…for example, in order to form stable complexes of Hg 2+ with macrocycles, crown ethers containing nitrogen or sulphur donor atoms should be used. [2][3][4][5][6] Blair et al have studied the binding selectivities of some caged crown ligands (containing nitrogen or sulphur donor atoms) towards Hg 2+ by electrospray ionisation mass spectrometry (ESI-MS). 7 complexes of Hg 2+ with crown ethers containing only oxygen donor atoms have also been studied, 5,6,8,9 but not by mass spectrometry techniques.…”

Rectangular Nanostructuring of Au(111) Surfaces by Self-Assembly of Size-Selected Thiacrown Ether Macrocycles

“…Among thioethers, thiacrown ethers (TCEs) are cyclic thioethers consisting of an alternance of sulfur atoms and (CH 2 ) n methylene bridges. , Saturated TCEs can be viewed as the sulfur counterparts of the well-known crown ethers and contain a variable number of sulfur atoms, each separated by a variable number of CH 2 groups. TCEs can behave as soft Lewis bases to interact selectively with metal ions such as Ag + , Hg 2+ , Cu + , and Pd 2+ and form inclusion complexes. , If the basic process involved in coordination of TCEs with metal ions is well-understood, − interaction of TCEs with metal substrates has not been explored yet. Because of the cyclic geometry of the TCE molecules, it can be expected that their adsorption on metal surfaces would take place via sulfur-metal interactions and result in self-organized domains of cavities with various sizes and shapes.…”