A new metal–organic framework based on cadmium(II) cations, di(p-carboxyphenyl)sulphone and 4,7-di(imidazol-1-yl)-2,1,3-benzothiadiazole was prepared, and its crystal structure was determined using single-crystal XRD analysis. MOF demonstrated bright luminescence with a maximum near 500 nm and quantum yield reaching 20%. In addition, this MOF demonstrated sensing properties towards antibiotics and a toxic natural polyphenol gossypol through effective luminescence quenching in an ethanol suspension. The determined detection limit for gossypol was among the lowest reported so far (0.65 µM), and did not significantly change in the interference experiments with cottonseed oil as background, indicating the possibility of using this MOF as a sensor for the detection and determination of gossypol in real-life samples.

Three isostructural metal–organic frameworks ([Ln₂(phen)₂(NO₃)₂(chdc)₂]·2DMF (Ln³⁺ = Y³⁺ for 1, Eu³⁺ for 2 or Tb³⁺ for 3; phen = 1,10-phenanthroline; H₂chdc = trans-1,4-cyclohexanedicarboxylic acid) were synthesized and characterized. The compounds are based on a binuclear block {M₂(phen)₂(NO₃)₂(OOCR)₄} assembled into a two-dime nsional square-grid network containing tetragonal channels with 26% total solvent-accessible volume. Yttrium (1)-, europium (2)- and terbium (3)-based structures emit in the blue, red and green regions, respectively, representing the basic colors of the standard RGB matrix. A doping of Eu³⁺ and/or Tb³⁺ centers into the Y³⁺-based phase led to mixed-metal compositions with tunable emission color and high quantum yields (QY) up to 84%. The bright luminescence of a suspension of microcrystalline 3 in DMF (QY = 78%) is effectively quenched by diluted cinnamaldehyde (cinnamal) solutions at millimolar concentrations, suggesting a convenient and analytically viable sensing method for this important chemical.

Here we describe the synthesis of a novel N,N’-bis(2,1,3-benzothiadiazol-4-yl)-1-phenylphosphanediamine (H₂L) and its zinc (II) and copper (I) coordination compounds [Zn₂L₂]·nC₇H₈ (1·nC₇H₈), [Zn₂(H₂L)₂Cl₄]·nC₇H₈ (2·nC₇H₈), and [Cu(H₂L)Cl]_n·nTHF (3·THF). According to single crystal X-ray diffraction analysis, H₂L ligand and its deprotonated species exhibit different coordination modes. An interesting isomerism is observed for the complexes [Zn₂(H₂L)₂Cl₄] (2a and 2b) that differ by the arrangement of H₂L. Both complexes possess internal cavities capable of incorporating toluene molecules. Upon toluene release, the geometry of 2b changes substantially, while that of 2a changes slightly. Due to the diverse structures, the compounds 1–3 reveal different photophysical properties. These results are discussed based on previously reported studies and DFT (density functional theory) calculations.

1H-Imidazole derivatives establish one of the iconic classes of ESIPT-capable compounds (ESIPT = excited state intramolecular proton transfer). This work presents the synthesis of 1-hydroxy-4-(2-hydroxyphenyl)-5-methyl-2-(pyridin-2-yl)-1H-imidazole (L^OH,OH) as the first example of ESIPT-capable imidazole derivatives wherein the imidazole moiety simultaneously acts as a proton acceptor and a proton donor. The reaction of L^OH,OH with chloroacetone leads to the selective reduction of the imidazolic OH group (whereas the phenolic OH group remains unaffected) and to the isolation of 4-(2-hydroxyphenyl)-5-methyl-2-(pyridin-2-yl)-1H-imidazole (L^H,OH), a monohydroxy congener of L^OH,OH. Both L^OH,OH and L^H,OH demonstrate luminescence in the solid state. The number of OH···N proton transfer sites in these compounds (one for L^H,OH and two for L^OH,OH) strongly affects the luminescence mechanism and color of the emission: L^H,OH emits in the light green region, whereas L^OH,OH luminesces in the orange region. According to joint experimental and theoretical studies, the main emission pathway of both compounds is associated with T₁ → S₀ phosphorescence and not related to ESIPT. At the same time, L^OH,OH also exhibits S₁ → S₀ fluorescence associated with ESIPT with one proton transferred from the hydroxyimidazole moiety to the pyridine moiety, which is not possible for L^H,OH due to the absence of the hydroxy group in the imidazole moiety.

A luminescent coordination polymer with the overall formula {[Zn(tr₂btd)(bpdc)]∙DMF}_n (where tr₂btd = 4,7-di(1H-1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole; bpdc = 4,4′-biphenyldicarboxylate) was synthesized and characterized by single-crystal and powder X-ray diffraction, thermogravimetric, infrared spectroscopy, and elemental analyses. Luminescent properties of the obtained compound were studied in detail both in the solid state and as a suspension in N,N-dimethylacetamide (DMA). It was found that {[Zn(tr₂btd)(bpdc)]∙DMF}_n exhibits bright turquoise luminescence with excellent quantum efficiency and demonstrates turn-on fluorescence enhancement effect upon soaking in DMA Al³⁺ solution. Fluorescence titration experiments were carried out and the detection limit for Al³⁺ ions was calculated to be 120 nM, which is among the lowest reported values for similar materials. Moreover, compound demonstrated excellent selectivity and reusability, and the mechanism of the response is discussed. These results indicate that {[Zn(tr₂btd)(bpdc)]∙DMF}_n is a promising probe for sensitive fluorescent Al³⁺ detection.

The photoluminescence of Au(I) complexes is generally characterized by long radiative lifetimes owing to the large spin-orbital coupling constant of the Au(I) ion. Herein, we report three brightly emissive Au(I) coordination compounds, 1, 2a, and 2b, that reveal unexpectedly short emission lifetimes of 10–20 ns. Polymorphs 2a and 2b exclusively exhibit fluorescence, which is quite rare for Au(I) compounds, while compound 1 reveals fluorescence as the major radiative pathway, and a minor contribution of a microsecond-scale component. The fluorescent behaviour for 1–2 is rationalized by means of quantum chemical (TD)-DFT calculations, which reveal the following: (1) S₀–S₁ and S₀–T₁ transitions mainly exhibit an intraligand nature. (2) The calculated spin-orbital coupling (SOC) between the states is small, which is a consequence of overall small metal contribution to the frontier orbitals. (3) The T₁ state features much lower energy than the S₁ state (by ca. 7000 cm⁻¹), which hinders the SOC between the states. Thus, the S₁ state decays in the form of fluorescence, rather than couples with T₁. In the specific case of complex 1, the potential energy surfaces for the S₁ and T₂ states intersect, while the vibrationally resolved S₁–S₀ and T₂–S₀ calculated radiative transitions show substantial overlap. Thus, the microsecond-scale component for complex 1 can stem from the coupling between the S₁ and T₂ states.