Coordination chemistry and photoswitching of dinuclear macrocyclic cadmium-, nickel-, and zinc complexes containing azobenzene carboxylato co-ligands
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
Authors: Klose, Jennifer; Severing, Tobias; Hahn, Peter; Jeremies, Alexander; Bergmann, Jens; Fuhrmann, Daniel; Griebel, Jan; Abel, Bernd; Kersting, Berthold
Abstract
The synthesis of mixed-ligand complexes of the type [M2L(mu-L')]+, where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand, L' is an azobenzene carboxylate co-ligand, and M = Cd(II), Ni(II) or Zn(II), is reported. A series of new complexes were synthesized, namely [M2L(mu-L')]+ (L' = azo-H, M = Cd (1), Ni (2); L' = azo-OH, M = Zn (3), Ni (4); L' = azo-NMe2, M = Zn (5), Cd (6), Ni (7); L' = azo-CO2Me, M = Cd (8), Ni (9)), and characterized by elemental analysis, electrospray ionization mass spectrometry (ESIMS), IR, UV-vis and NMR spectroscopy (for diamagnetic Zn and Cd complexes) and X-ray single crystal structure analysis. The crystal structures of 3' and 5-8 display an isostructural series of compounds with bridging azobenzene carboxylates in the trans form. The paramagnetic Ni complexes 2, 4 and 7 reveal a weak ferromagnetic exchange interaction with magnetic exchange coupling constant values between 21 and 23 cm(-1) (H = -2JS(1)S(2)). Irradiation of 1 with lambda = 365 nm reveals a photoisomerization of the co-ligand from the trans to the cis form.
Proton-Sponge-Like Superbases Built on the Benzo[h]quinoline Platform
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Authors: Ozeryanskii, Valery A.; Pozharskii, Alexander F.
Abstract
6,10-Bis(dimethylamino)benzo[h]quinoline (6) and its reverse counterpart, the 6,7-isomer 7 (a pyridine-extended proton sponge), have been prepared in a three-step synthetic protocol starting from 1,5-bis- and 1,8-bis(dimethylamino)naphthalenes, respectively, through azo coupling and Skraup cyclisation reactions. These novel polyfunctional nitrogen bases demonstrate excellent chelation ability towards protons and even Pd-II, and behave as kinetically active (6) and kinetically inactive (7) compounds, as demonstrated by NMR transprotonation experiments in DMSO. Single-crystal X-ray diffractometry was used to characterise rare types of chelated [NHN](+) hydrogen bonds and to reveal the location of the proton in protonated 6 (H+ between NMe2 and the pyridine nitrogen) and its zwitterionic azo-dye precursor 8Z (H+ between NMe2 and the azo group). Experimental pK(a) values measured in DMSO show that 6 and 7 are strong bases, and the strength of the basicity of the 6,10-isomer 6 (pK(a) = 8.1) places this benzo[h]quinoline in the category of heterocyclic superbases.