We report here the synthesis of an ultrasound induced multi-responsive, fluorescent, conductive metallogel based on a non-fluorescent citric acid derived ligand (1), LiOH and Cd(OAc)2 in DMF.
With intent to fine tune the morphological and photophysical properties, three novel AIE luminogens (BQ1-BQ3) based on quinoline-BODIPY have been synthesized. A judicious choice of substituents (-H, -CH3, -OCH3) in these systems led to nanoballs in BQ1 and BQ2, while in BQ3 it led to reticulated nanofibers with diverse photophysical behaviours.
A novel chiral coordination polymeric gel based on an amino acid derived symmetrical ligand, specific base, and Zn(2+) has been described. Zn(2+) induced conformational reorganization in the ligand leads to gelation via J-aggregated helical fibres. The vital role played by π-π stacking in gelation has been monitored by fluorescence and NMR spectroscopy.
Progelator complex Zn-TRPA-2 undergoes Cl(-) triggered gelation to afford ZTP2G, while Zn-TRPA-2 capped Au-NPs under similar conditions gave another gel GNZTP2G which also represents a rare nano-composite metallogel. When Zn-TRPA-2 was triggered by Cl(-) and NO3(-) simultaneously, crystals of demetalated species NA-TRPA-2 grew inside the ZTP2G matrix. Interestingly, GNZTP2G exhibits superior viscoelastic properties over ZTP2G.
L-leucine derived ligand (H(2)L(L-leu)), KOH, and Ni(II) salt in 2:2:1 ratio self-assembled into a rather large (approximately 13 A) supramolecular assembly with the formula [K{Ni(HL(L-leu))(2)}(3)](+) (1). Structural characterization showed three [Ni(HL(L-leu))(2)] units encapsulated K(+) similar to organic crown ethers/cryptand. Substituting Ni(II) with Cu(II) and K(+) with Na(+) in the above reaction resulted in a set of structurally identical assemblies with the general formula [M'{M(HL(L-leu))(2)}(3)](+), where M' is either K(+) or Na(+) and M is either Cu(II) or Ni(II); [Na{Ni(HL(L-leu))(2)}(3)]ClO(4) (2), Na{Ni(HL(L-leu))(2)}(3)]OTf (3), [K{Cu(HL(L-leu))(2)}(3)]ClO(4) (4), [Na{Cu(HL(L-leu))(2)}(3)]ClO(4) (5), [K{Cu(HL(L-leu))(2)}(3)]NO(3) (6). Electrospray Ionization (ESI)-mass spectra of the assemblies in MeOH showed the retention of assemblies in solution. Visible spectroscopic studies showed retention of assembly 1 in N,N-dimethylformamide (DMF) which is stable even after the addition of 5 equiv of [18]-crown-6. The assemblies in 2-6 show various degrees of dissociation to [M(HL(L-leu))(2)] and M', in stronger H-bonding methanol. The dissociation can be reversed upon addition of excess KNO(3)/NaNO(3) salt. Structural characterization of [Cu(HL(L-leu))(2)(MeCN)] (7) along with its transformation to [K{Cu(HL(L-leu))(2)}(3)](+) in the presence of K(+) salt demonstrated that the assembly formation proceeds through an alkali metal ion induced ligand reorientation within the [Cu(HL(L-leu))(2)] units which is further stabilized by six strong H-bonds holding the assembly. Interestingly, visible spectra of 1 and 2 shows that minor structural changes caused by replacing K(+) with Na(+) is sufficient to shift the d-d transition of Ni(II) by approximately 70 nm, thereby providing an indirect way of distinguishing K(+) and Na(+), none of which have spectroscopic signature in the visible range.
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