Syntheses and Crystal Structures of Mercury(II) and Copper(II) Complexes of an 18‐Membered NS₄‐Macrocycle

Abstract

An 18-membered NS 4 -macrocycle was employed, and its complexation behaviors with hard and soft metal ions were investigated. Reactions of L with mercury(II) nitrate and thiocyanate afforded endocyclic mononuclear complexes [Hg(L)(NO 3 ) 2 ] (1) and [Hg(L)(SCN) 2 ] (2), respectively, with anion coordinations. In the nitrato complex 1, the mercury(II) center is six-coordinate, being bound to three S donors and one pyridine N atom in L, and the coordination sphere is completed by two monodentate nitrate ions from both sides of the macrocyclic plane adopting a distorted octahedral geometry. The thiocyanato complex 2, which contains two crystallographically independent but almost isostructural complex units is five-coordinate, being bound to NS 2 donors in L and two monodentate thiocyanate ions on the same side of the bound macrocycle unlike 1, adopting a distorted square pyramidal geometry. Reaction of L with CuCl 2 Á 2H 2 O yielded a dark-green bis(macrocycle) trinuclear complex, [Cu 3 (L) 2 Cl 6 ] Á 0.5CH 2 Cl 2 (3), in which two endocyclic monocopper (II) complex units are linked by an exocyclic one Cu and two bridging Cl atoms. In 3, interestingly, the local coordination environments of the three copper(II) atoms are different, with four, five, or six coordination, adopting a distorted square pyramidal, tetrahedral, or octahedral geometry, respectively. From these results, it is found that the ditopic ligand L reacts with both soft and hard metal-ion species to give diverse types of endocyclic complexes whose structures are also dependent on the anions used.

Group 12 Metal Complexes of an 18-Membered N2O2S2 Macrocycle Incorporating Two Pyridines: First Examples of an Infinite Mercury(I) Complex and a Dumbbell-Shaped Heteronuclear Complex with a Macrocyclic Ligand

“…Previously, our group reported three examples of cluster-linked homonuclear dumbbell-type macrocyclic complexes (Chart b): [(CuLCl) 2 (μ-CuCl 4 )] (L = 18-membered NS 4 macrocycle) (Chart a), [(HgL) 2 (μ-Hg 2 Br 6 )] (L = 20-membered NO 2 S 3 macrocycle) (Chart b), and [(CdL) 2 (μ-Cd 4 I 12 )] (L= 20-membered NO 2 S 3 macrocycle) (Chart c) . However, our subsequent efforts to prepare heteronuclear dumbbell complexes by employing diverse types of macrocycles, including thiamacrocycles, were not successful.…”

Direct Observation and Control of Ultrafast Photoinduced Twisted Intramolecular Charge Transfer (TICT) in Triphenyl-Methane Dyes

“…28,29 In MG and its derivatives (LMG and MGCB), the combination of two dimethylanilines and one phenyl ring tethered by a central carbon bridge produces more complex absorption spectra. Figure 2A shows the UV/vis spectra of 1 mM MG (black line), 15 mM LMG (blue line), and 20 mM MGCB (red line) in methanol.…”

Solvent-Dependent Formations of Supramolecular Isomers and a Single-Crystal to Single-Crystal Transformation from a Cyclic Dimer Complex to a One-Dimensional Coordination Polymer

“…Overall, the octahedral CuO 4 N 2 coordination cores with different configurations show distinct roles: a corner piece in 1 , while a linker unit in 2 . Most copper­(II) (d 9 ) complexes with Jahn–Teller distortion , undergo elongation of the axis, and it may occur in the bidentate ligands including hfac – ion whose bite angle is large. Similarly, the geometry of the Cu1 atoms in 1 and 2 is elongated octahedral; axial bond lengths are 2.279(3) Å (Cu1–O1) and 2.345(3) Å (Cu1–O3) for 1 and 2.261(2) Å (Cu1–O2) and 2.300(2) Å (Cu1–O3) for 2 , which are longer than those of the four equatorial bonds (1.982(3)–2.002(3) Å for 1 and 1.992(2)–2.011(2) Å for 2 ).…”