New Family of Silver(I) Complexes Based on Hydroxyl and Carboxyl Groups Decorated Arenesulfonic Acid: Syntheses, Structures, and Luminescent Properties

Self-assembly of silver­(I) salts and three ortho-hydroxyl and carboxyl groups decorated arenesulfonic acids affords
the formation of nine silver­(I)-sulfonates, (NH4)·[Ag­(HL1)­(NH3)­(H2O)] (1), {(NH4)·[Ag3(HL1)2(NH3)­(H2O)]}n (2), [Ag2(HL1)­(H2O)2]n (3), [Ag2(HL2)­(NH3)2]·H2O (4), [Ag­(H2L2)­(H2O)]n (5), [Ag2(HL2)]n (6),
[Ag3(L3)­(NH3)3]n (7), [Ag2(HL3)]n (8), and [Ag6(L3)2(H2O)3]n (9) (H3L1 = 2-hydroxyl-3-carboxyl-5-bromobenzenesulfonic acid, H3L2 = 2-hydroxyl-4-carboxylbenzenesulfonic acid, H3L3 = 2-hydroxyl-5-carboxylbenzenesulfonic acid),
which are characterized by elemental analysis, IR, TGA, PL, and single-crystal
X-ray diffraction. Complex 1 is 3-D supramolecular network
extended by [Ag­(HL1)­(NH3)­(H2O)]− anions and NH4+ cations. Complex 2 exhibits 3-D host–guest framework which encapsulates
ammonium cations as guests. Complex 3 presents 2-D layer
structure constructed from 1-D tape of sulfonate-bridged Ag1 dimers
linked by [(Ag2)2(COO)2] binuclear units. Complex 4 exhibits 3-D hydrogen-bonding host–guest network
which encapsulates water molecules as guests. Complex 5 shows 3-D hybrid framework constructed from organic linker bridged
1-D Ag–O–S chains while complex 6 is 3-D
pillared layered framework with the inorganic substructure constructing
from the Ag2 polyhedral chains interlinked by Ag1 dimers and sulfonate
tetrahedra. The hybrid 3-D framework of complex 7 is
formed by L3– trianions
bridging short trisilver­(I) sticks and silver­(I) chains. Complex 8 also presents 3-D pillared layered framework, and the inorganic
layer substructure is formed by the sulfonate tetrahedrons bridging
[(Ag1O4)2(Ag2O5)2]∞ motifs. Complex 9 represents the first
silver-based metal-polyhedral framework containing four kinds of coordination
spheres with low coordination numbers. The structural diversities
and evolutions can be attributed to the synthetic methods, different
ligands and coordination modes of the three functional groups, that
is, sulfonate, hydroxyl and carboxyl groups. The luminescent properties
of the nine complexes have also been investigated at room temperature,
especially, complex 1 presents excellent blue luminescence
and can sensitize Tb­(III) ion to exhibit characteristic green emission.