Syntheses and Structures of Mononuclear, Dinuclear
and Polynuclear Silver(I) Complexes of 2‑Pyrazole-Substituted
1,10-Phenanthroline Ligands
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Abstract
A series of mononuclear, dinuclear and polynuclear silver(I)
complexes
(<b>1</b>–<b>6</b>) bearing 2-pyrazole-substituted
1,10-phenanthroline derivatives (<b>L</b><sup><b>1</b></sup>, <sup><b>F</b></sup><b>L</b><sup><b>1</b></sup>, <b>L</b><sup><b>2</b></sup>) have been synthesized
and characterized by <sup>1</sup>H and <sup>13</sup>C NMR, IR spectroscopy,
elemental analysis, and single crystal X-ray diffraction. Reaction
of <b>L</b><sup><b>1</b></sup> (<b>L</b><sup>1</sup> = 2-(3,5-dimethylpyrazol-1-yl)-1,10-phenanthroline) with AgClO<sub>4</sub> or AgBF<sub>4</sub> afforded two dinuclear silver(I) complexes
[Ag<sub>2</sub>(<b>L</b><sup><b>1</b></sup>)<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub> (<b>1</b>) and [Ag<sub>2</sub>(<b>L</b><sup><b>1</b></sup>)<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>](BF<sub>4</sub>)<sub>2</sub> (<b>2</b>), in which two [Ag<b>L</b><sup><b>1</b></sup>(CH<sub>3</sub>CN)]<sup>+</sup> units are linked by
Ag···Ag interaction (Ag···Ag separation:
3.208(2) and 3.248(1) Å, respectively). A one-dimensional polymer
{[Ag<b>L</b><sup><b>1</b></sup>](BF<sub>4</sub>)}<sub>∞</sub> (<b>3</b>) consisting of an infinite ···Ag···Ag···Ag···
chain (Ag···Ag separation: 3.059(1) Å), as well
as a dinuclear complex [Ag<sub>2</sub>(ClO<sub>4</sub>)<sub>2</sub>(<b>L</b><sup><b>1</b></sup>)<sub>2</sub>] (<b>4</b>) in which the perchlorate anions instead of solvents are involved
in the metal coordination, have also been obtained. The mononuclear
complex [Ag(<sup><b>F</b></sup><b>L</b><sup><b>1</b></sup>)<sub>2</sub>](BF<sub>4</sub>) (<b>5</b>) was synthesized
from <sup><b>F</b></sup><b>L</b><sup><b>1</b></sup> (<sup><b>F</b></sup><b>L</b><sup><b>1</b></sup> = 2-(3,5-bis(trifluoromethyl)pyrazol-1-yl)-1,10-phenanthroline)
and AgBF<sub>4</sub>, while the dinuclear [Ag<sub>2</sub>(BF<sub>4</sub>)<sub>2</sub>(<b>L</b><sup><b>2</b></sup>)<sub>2</sub>] (<b>6</b>) was isolated from <b>L</b><sup><b>2</b></sup> (<b>L</b><sup><b>2</b></sup> = 2-[<i>N</i>-(3-methyl-5-phenylpyrazole)]-1,10-phenanthroline). The photoluminescence
properties of the ligands and complexes <b>1</b>–<b>6</b> have been studied both in the solid state and in solution
