A rationally designed probe L, which consists of both cation and anion binding sites, is capable of displaying interesting aggregation induced emission (AIE) properties. L not only can sense Al(3+) and Zn(2+) through selective turn-on fluorescence responses in 9 : 1 methanol-HEPES buffer (5 mM, pH 7.3; 9 : 1, v/v) medium due to metal ion triggered AIE activity, but also can distinguish them through individual emission signals. L can also detect Cu(2+) in mixed buffer medium and F(-) in acetonitrile through sharp colorimetric responses. All the sensing processes are conspicuous through the naked eye. A theoretical study strongly backed the proposed sensing mechanisms.
A meta-phenylenediamine-based disubstituted bis-urea receptor L1 with electron-withdrawing 3-chloro and electron-donating 4-methylphenyl terminals has been established as a potential system to fix and efficiently capture atmospheric CO as air-stable entrapment of an unprecedented {CO-(HO)-CO} cluster (complex 1a) within its tetrameric long straight pillar-like assembly entirely sealed by n-TBA cations via formation of a barrel-type architecture. L1 and its isomeric 4-bromo-3-methyl disubstituted bis-urea receptor L2 have been found to entrap similar kinds of water-free naked sulfate-sulfate double anion (complexes 1b and 2a) by cooperative binding of urea moieties inside the two pairs of the inversion-symmetric linear tetrameric barrel of L1 and L2, respectively. On the other hand, in the presence of excess halides, L1 self-assembles to form hexa-coordinated fluoride complex 1c and tetra-coordinated bromide complex 1d, while L2 self-assembles to form penta-coordinated fluoride complex 2b in the solid state via semicircular receptor architectures and non-cooperative H-bonding interactions of urea moieties.
meta-Phenylenediamine based two linear bis-urea anion receptors, L
1
(meta-nitro) and L
2
(para-nitro),
have been synthesized which showed strong binding affinities toward
halides as well as planar and tetrahedral oxyanions. In the presence
of excess fluoride anion, L
1
self-assembles
to entrap a cyclic fluoride–water tetrameric cluster within
its tetrameric pillar-like assembly of each urea arm (complex 1a). In the presence of sulfate anion, L
1
self-assembles in an identical fashion to entrap
the bigger tetrahedral anion (complex 1b), whereas two
urea moieties of two different receptor molecules of L
1
have been structurally authenticated to
be sufficient to stabilize the simple Y-shaped acetate anion in complex 1c. On the other hand, receptor L
2
, with a bis(para-nitro urea) functional group,
especially in the presence of sulfate anion, self-assembles like long
straight pillars entrapping sulfate–water–sulfate cluster
{SO4
2–-(H2O)3-SO4
2–} (complex 2a). Additionally, L
2
forms a host–guest assembly
with the cation and solvent (DMSO) coordinated bromide anion (complex 2b) when treated with excess bromide anion as n-tetrabutylammonium salt. All the complexes have been characterized
by powder X-ray diffraction and 1H NMR and 13C NMR spectroscopy, which are in full support and consistent with
solid-state single crystal X-ray diffraction results.
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