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Homochiral Metal–Organic Frameworks of Lead(II) and Cadmium(II) Constructed by Amino Acid-Functionalized Isophthalic Acids: Synthesis, Structure Diversity, and Optical Properties
journal contribution
posted on 2019-12-13, 16:43 authored by Yafang Ge, Baoshan Teng, Lulu Lv, Rui Chen, Benlai WuOn the basis of amino acid-functionalized isophthalic
acids, four
interesting homochiral metal–organic frameworks (HMOFs), namely,
{[Pb2(HL1)2]·11H2O}n (1), {[Pb2(HL2)2]·12H2O}n (2), {[Cd6(L2)4(H2O)11]·6H2O}n (3), and [Pb(HL3)]n (4), were constructed
(H3L1 = (S)-5-(((1-carboxyethyl)amino)methyl)isophthalic
acid, H3L2 = (S)-5-(((1-carboxy-3-methylbutyl)amino)methyl)isophthalic
acid, and H3L3 = (S)-5-(((1-carboxy-2-phenylethyl)amino)methyl)isophthalic
acid). In 1, 2, and 4, all
PbII ions have hemidirected coordination geometries despite
the difference in coordination number, and ligands H3L1–H3L3 in negative bivalent zwitterionic
forms adopt various coordination modes to bridge PbII centers
into two- and three-dimensional (2D–3D) coordination polymers,
respectively. Both 1 and 2 contain two independent
63-topological homochiral layers which further form a unique
hydrogen-bonded double-layered HMOF with the stereochemically active
lone pairs of all PbII ions pointing inward and the hydrophobic
side arms of amino acid groups being located on both sides. For 4, it is a 3D helicate of (42·6·83)(42·63·8) topology, and the
resulting one-dimensional (1D) channels are occupied by the hydrophobic
benzyls of amino acid groups in (HL3)2– ligands. Coordination polymer 3 is an intriguing HMOF
that contains two independent 2D double-layered (63)(65·8)-topological helicates with alternating distribution
of 1D hydrophilic and hydrophobic helical channels. In 3, all hydrophilic helical channels are occupied by water molecules,
while all hydrophobic helical channels are filled by the isobutyls
of amino acid groups. Remarkably, these chiral tricarboxylic ligands
not only have versatile coordination modes in the construction of
HMOFs, but also subtly regulate the crystal structures through the
different hydrophobic side arms of amino acids implanted in these
ligands. Furthermore, the thermal stabilities and solid-state optical
properties, including CD spectra, and nonlinear optical and luminescent
properties of these complexes were also investigated. Interestingly
enough, in our example, it was found that hemidirected, five-coordinate
PbII compounds perhaps have stronger emission than those
hemidirected four- or six-coordinate PbII compounds.
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Keywords
six-coordinate Pb II compoundsacid groupsbridge Pb II centersbivalent zwitterionic formsH 3 L 1H 3 L 2H 3 L 3side armsHLcoordination modesCoordination polymer 3Pb II ionsPb II compoundsacid-functionalized isophthalic acidshemidirected coordination geometries3 D helicatechiral tricarboxylic ligandstopological homochiral layershelical channelsH 2 OAmino Acid-Functionalized Isophthalic Acidshydrogen-bonded double-layered HMOF
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