Premium
Mono‐, Di‐, and Polymeric Pyridinoylhydrazone Zn II Complexes: Structure and Photoluminescent Properties
Author(s) -
Borbone Fabio,
Caruso Ugo,
Concilio Simona,
Nabha Shiran,
Panunzi Barbara,
Piotto Stefano,
Shikler Rafi,
Tuzi Angela
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501132
Subject(s) - chemistry , denticity , pyridine , moiety , photoluminescence , density functional theory , crystal structure , zinc , crystallography , molecule , nitrogen atom , photochemistry , stereochemistry , computational chemistry , group (periodic table) , medicinal chemistry , organic chemistry , physics , optics
A series of zinc complexes with tridentate pyridinoylhydrazone ligands bearing two different end groups and coordinated pyridine molecules were synthesized and characterized. Crystal structures with mono‐, di‐, and polymeric arrangements were obtained, depending on the position of the pyridinoyl nitrogen atom. Direct involvement of the pyridinoyl moiety in the coordination to the metal was observed when the nitrogen was in the ortho or meta position. The meta derivatives led to 1D polymers with the same coordination environment, regardless of the bulkiness of the end group. In this case, unprecedented solid‐state photoluminescence quantum yields were recorded. In the ortho ligands, the further bidentate N , N site involving the pyridinoyl nitrogen atom was able to coordinate a further zinc acetate unit. Molecular and periodic calculations were performed within density functional theory (DFT) to rationalize the photophysical behavior. Excellent agreement between the theoretical and experimental absorptions was observed. The HOMOs and LUMOs of the complexes were investigated both in the solid state and in solution.