ABSTRACT
The macrocyclic ligand calix[4]arene (L1) and its sulphur-containing analogue thia[4]calixarene (L2) are promising precursors for functional molecular materials as they offer rational functionalization with various organic groups. Here, we present the first example of lanthanide-based coordination polymers built from the macrocyclic thiacalix[4]arene backbone bearing four carboxylic moieties, namely, ligand H4L3. The combination of H4L3 with the Tb3+ and Dy3+ cations led to the formation of 1D ladder-type coordination polymers with the formula [LnIIIHL3DMF3]·(DMF) (where DMF = dimethylformamide and Ln = Tb or Dy, denoted as HL3-Tb and HL3-Dy), which resulted from the coordination of the lanthanide cations with the partially deprotonated ligand HL33- that behaved as a T-shape connector. The coordination sphere around the metal was completed by the coordinated DMF solvent molecules. By combining both Tb3+ and Dy3+ cations, isostructural heterobimetallic solid solutions HL3-Tb1- x Dy x were also prepared. HL3-Tb and HL3-Dy showed visible light photoluminescence originating from the f-f electronic transitions of pale green emissive Tb3+ and pale yellow emissive Dy3+ with efficient sensitization by the functionalized thia[4]calixarene ligand HL3. In the HL3-Tb1- x Dy x solid solutions, the Tb/Dy ratio governed both the emission colour as well as the emission quantum yield, which reached even 28% at room temperature for HL3-Tb. Moreover, HL3-Dy exhibited a slow magnetic relaxation effect related to the magnetic anisotropy of the dodecahedral Dy3+ complexes, which were well isolated in the crystal lattice by expanded organic spacers.
ABSTRACT
The article contains curriculum vitae of W. Griesinger and an analysis of the clinical-psychopathological approach developed by him for studying illnesses and their systematization. The stages of psychosis' progression in dynamics are shown. A clinical description of primary emerged dementia made by W. Griesinger as well as a description of the status of Grubelsucht, first discovered by the psychiatrist, are presented. The article emphasizes W. Griesinger' priority in the determination of reflexes' exclusive role in the appearance and further development of all types of mental disorders. W. Griesinger's conviction in the necessity of more close interaction of neurology and psychiatry is highlighted.
Subject(s)
Psychiatry/history , Psychopathology/history , Dementia/history , Germany , History, 19th Century , Humans , Neurology/history , Psychotic Disorders/history , ReflexABSTRACT
Sergey Sergeievich Korsakov (1854-1900) was an outstanding Russian psychiatrist, founder of the Moscow psychiatric school, a talented clinician and teacher, and a supporter of the nosological approach in the understanding and systematization of psychiatric illnesses. He described alcoholic polyneuritis with distinctive mental symptoms, which later on was coined "Korsakov's disease." He was the first to give a clear account of paranoia. Korsakov was a leader in more humane patient management by applying no-restraint principles.
