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Steric and Electronic Effects on the Structure and Photophysical Properties of Hg(II) Complexes
Francisco Sánchez-Férez1, Joaquim Ma Rius-Bartra1, Teresa Calvet2
1Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain.
Abstract:
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.
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