Open AccessSteric and Electronic Effects on the Structure and Photophysical Properties of Hg(II) Complexes
Author(s) -
Francisco Sánchez-Férez,
Joaquim Ma Rius-Bartra,
Teresa Calvet,
Mercè Font-Bardı́a,
Josefina Pons
Publication year - 2021
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.0c03640
Subject(s) - chemistry , steric effects , dimer , crystallography , electronic effect , electronic structure , amine gas treating , bipyridine , crystal structure , terpyridine , metal , stereochemistry , computational chemistry , organic chemistry
Since many factors influence the coordination around a metal center, steric and electronic effects of the ligands mainly determine the connectivity and, thus, the final arrangement. This is emphasized on Hg(II) centers, which have a zero point stabilization energy and, thus, a flexible coordination environment. Therefore, the unrestricted Hg(II) geometry facilitates the predominance of the ligands during the structural inception. Herein, we synthesized and characterized a series of six Hg(II) complexes with general formula (Hg(Pip) 2 (dPy)) (Pip = piperonylate, dPy = 3-phenylpyridine (3-phpy) ( 1 ), 4-phenylpyridine (4-phpy) ( 2 ), 2,2′-bipyridine (2,2′-bipy) ( 3 ), 1,10-phenanthroline (1,10-phen) ( 4 ), 2,2′:6′,2′-terpyridine (terpy) ( 5 ), or di(2-picolyl)amine (dpa) ( 6 )). The elucidation of their crystal structures revealed the arrangement of three monomers ( 3 , 5 , and 6 ), one dimer ( 4 ), and two coordination polymers ( 1 and 2 ) depending on the steric requirements of the dPy and predominance of the ligands. Besides, the study of their photophysical properties in solution supported by TD-DFT calculations enabled us to understand their electronic effects and the influence of the structural arrangement on them.