Effects of transition metal cations and temperature on the luminescence of a 3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H-pyrrole-2-olate anion

Two new mononuclear complexes based on the anion 3-cyano-4-dicyanomethylene-5-oxo-4,5-dihydro-1H-pyrrol-2-olate (C8HN4O2- = HA(-)) and Mn2+ or Zn2+ cations, namely [Mn(HA)(2)(H2O)(4)]center dot 2H(2)O (1) and [Zn(HA)(2)(H2O)(4)] (2), were synthesized and characterized by single-crystal X-ray diffraction and photoluminescence spectroscopy. Complexes 1 and 2 crystallize in the triclinic space group P1. Units [M(HA)(2)(H2O)(4)] (M = Mn, Zn) are the basic building blocks in both 1 and 2 crystal structures. The metal cation, located on an inversion center, is bound to two nitrogen atoms of two HA(-) and four water oxygen atoms. Units [M(HA)(2)(H2O)(4)] are connected by pi-pi stacking interactions between anions HA(-) and by hydrogen bonds to form a 3D crystal structure. Complexes 1 and 2 are isostructural with previously reported complexes [Cd(HA)(2)(H2O)(4)]center dot 2H(2)O and [Cu(HA)(2)(H2O)(4)], respectively. A comparison between the luminescence properties of isostructural complexes confirms that the incompletely filled 3d subshell (3d(5), 3d(9)) of a divalent metal cation is a key factor leading to the total luminescence quenching of anion HA(-) upon complexation with metal cations. Salts M(HA)(2) (M = Mn, Cd, Cu, or Zn) adsorbed on cellulose paper display thermo-sensitive luminescence. The luminescence is due to HA(-) anions. The intensity of the luminescence peak reversibly decreases by 6-7 times upon heating from 27 up to 123 degrees C.