Supramolecular Optimization of Sensory Function of a Hemicurcuminoid through Its Incorporation into Phospholipid and Polymeric Polydiacetylenic Vesicles: Experimental and Computational Insight.

This work presents the synthesis of a new representative of hemicurcuminoids with a nonyloxy substituent () as a fluorescent amphiphilic structural element of vesicular aggregates based on phosphatidylcholine (PC), phosphatidylserine (PS), and 10,12-pentacosadiynoic acid (PCDA). Both X-ray diffraction analysis of the single crystal and H NMR spectra of in organic solvents indicate the predominance of the enol-tautomer of . DFT calculations show the predominance of the enol tautomer in supramolecular assemblies with PC, PS, and PCDA molecules.

Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb-Luminescence via Upper-Rim Substitution.

The present work introduces the series of thiacalix[4]arenes (HL) bearing different upper-rim substituents (R = H, Br, NO) for rational design of ligands providing an antenna-effect on the NIR Yb-centered luminescence of their Yb complexes. The unusual inclusive self-assembly of HL (Br) through Brπ interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb:2HL] leads to efficient sensitizing of the Yb luminescence for HL (Br, NO), while poor sensitizing is observed for ligand HL (H).

Role of PSS-based assemblies in stabilization of Eu and Sm luminescent complexes and their thermoresponsive luminescence.

The present work introduces self-assembled polystyrenesulfonate (PSS) molecules as soft nanocapsules for incorporation of Eu-Sm complexes by the solvent exchange procedure. The high levels of Eu- and Sm-luminescence of the complexes derives from the ligand-to-metal energy transfer, in turn, resulted from the complex formation of Euand Sm ions with the three recently synthesized cyclophanic 1,3-diketones. The structural features of the ligands are optimized for the high thermal sensitivity of Eu- luminescence in DMF solutions.

Single Excited Dual Band Luminescent Hybrid Carbon Dots-Terbium Chelate Nanothermometer.

The report introduces hybrid polyelectrolyte-stabilized colloids combining blue and green-emitting building blocks, which are citrate carbon dots (CDs) and [TbL] chelate complexes with 1,3-diketonate derivatives of calix[4]arene. The joint incorporation of green and blue-emitting blocks into the polysodium polystyrenesulfonate (PSS) aggregates is carried out through the solvent-exchange synthetic technique. The coordinative binding between Tb centers and CD surface groups in initial DMF solutions both facilitates joint incorporation of [TbL] complexes and the CDs into the PSS-based nanobeads and affects fluorescence properties of [TbL] complexes and CDs, as well as their ability for temperature sensing.

Terbium(III)-thiacalix[4]arene nanosensor for highly sensitive intracellular monitoring of temperature changes within the 303-313 K range.

The work introduces hydrophilic PSS-[Tb(TCAn)] nanoparticles to be applied as highly sensitive intracellular temperature nanosensors. The nanoparticles are synthesized by solvent-induced nanoprecipitation of [Tb(TCAn)] complexes (TCAn - thiacalix[4]arenes bearing different upper-rim substituents: unsubstituted TCA1, tert-buthyl-substituted TCA2, di- and tetra-brominated TCA3 and TCA4) with the use of polystyrenesulfonate (PSS) as stabilizer. The temperature responsive luminescence behavior of PSS-[Tb(TCAn)] within 293-333 K range in water is modulated by reversible changes derived from the back energy transfer from metal to ligand (M* → T) correlating with the energy gap between the triplet levels of ligands and resonant D level of Tb ion.

Correction: A simple synthetic approach to enhance the thermal luminescence sensitivity of Tb complexes with thiacalix[4]arene derivatives through upper-rim bromination.

Correction for 'A simple synthetic approach to enhance the thermal luminescence sensitivity of Tb3+ complexes with thiacalix[4]arene derivatives through upper-rim bromination' by Sergey N. Podyachev, et al., Dalton Trans.

A simple synthetic approach to enhance the thermal luminescence sensitivity of Tb complexes with thiacalix[4]arene derivatives through upper-rim bromination.

The present work for the first time reports an application of the thiacalix[4]arene scaffold for the preparation of Tb3+ complexes possessing high thermal luminescence sensitivity in the physiological temperature range of 20-50 °C. Non-substituted thiacalix[4]arenes form luminescent complexes with Tb3+ ions, but they do not reveal any meaningful thermal sensitivity. To solve this problem, an upper-rim bromination of thiacalix[4]arenes, as well as distal bromination along with the embedding of two 1,3-diketone substituents are proposed as new simple synthetic approaches to enhance the thermal luminescence sensitivity of the Tb3+ complexes.

Structural and photophysical properties of Tb-tetra-1,3-diketonate complexes controlled by calix[4]arene-tetrathiacalix[4]arene scaffolds.

The present work highlights the key aspects of the influence of calix[4]arene and tetrathiacalix[4]arene scaffolds on the structural and photophysical properties of Tb3+ complexes with tetra-1,3-diketone derivatives of the macrocycles in DMF solutions. The equilibrium forms of Tb3+ complexes with unsubstituted and functionalized by acetylacetonyl groups at the upper rim of calix[4]arenes and thiacalix[4]arenes are revealed from UV-, NMR, MALDI TOF mass spectroscopy, quantum-chemical calculations at the DFT level and luminescence spectroscopy data. In alkaline DMF solutions, the ligands form predominantly 1 : 1 complexes with Tb3+ ions.

Polystyrenesulfonate-coated nanoparticles with low cytotoxicity for determination of copper(II) via the luminescence of Tb(III) complexes with new calix[4]arene derivatives.

The authors describe new ligands with two 1,3-diketone groups and two heteroaromatic (pyridyl or quinolyl) moieties embedded to the upper and lower rims of dibromo-substituted calix[4]arene scaffold. The ligands bind Tb(III) ions in alkaline DMF solutions to form 1:1 complexes. The strong Tb(III)-centered luminescence (with excitation/emission peaks at 330/545 nm) of the complexes results from efficient ligand-to-metal energy transfer.