Combined Experimental and Theoretical Studies on the Rubbing-Induced Fluorescence Behavior of a Luminophore in the Solid State.

It is intricate to break and make chemical bonds in solid states compared to their solution states, so it is imperative to ascertain green proficient approaches by regulating the solid-state structures and their related material properties. Here, the rubbing-induced photoluminescence behavior of a luminophore (RIL) of the benzimidazole family in the solid state has been accomplished. Interestingly, upon gentle rubbing or mere scratching, solid-state fluorescence from the nonemissive pristine RIL was observed due to the aggregation-induced emission (AIE) phenomenon in the solid state, for which the phenolic moiety is present in the molecule and is accountable. The structure-property relationship of RIL and the mechanism responsible for this solid-state fluorescence characteristics have been explained with the help of experimental (using the single-crystal structure, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) images, etc.) and theoretical (by DFT and TDDFT) studies. The crystal arrangements with different stacking interactions and the SEM images after being rubbed revealed that the mechanical force- or pressure-induced slight deformation in the crystal arrangement notably facilitated the strong emission in the solid state. This rubbing-induced solid-state fluorescence in a new luminophore (RIL) through stacking of layers restricting the molecular motion has been developed here for the first time, and it can be explicitly employed in steganography techniques for data security. This present study will open up a new insight into the use of this RIL as a solid-state smart material for data security in coding devices in the future, and this developed approach may be helpful to ameliorate the design of new-generation smart materials by modifying the structure to attain other characteristics.

Encapsulation and Stabilization of a Donor-Acceptor Stenhouse Adduct Isomer in Water Inside the Blue Box: A Combined Experimental and Theoretical Approach.

We synthesized two types of donor-acceptor Stenhouse adducts (DASAs), a new type of photochromic molecules showing dual color in two different isomeric forms in solution phase, using Meldrum acid (DASA-Mel) and barbituric acid (DASA-Bar), along with a naphthalimide derivative to obtain interesting fluorescence properties. DASA-Mel was found to have fast photochromic conversion in comparison to DASA-Bar, evident from ultraviolet-visible (UV-vis) and fluorescence spectroscopic studies. The colored form of DASA-Mel was encapsulated inside the water-soluble Stoddart's blue box and became soluble in water much faster than DASA-Bar. Interestingly, the competitive encapsulation experiment showed that DASA-Mel was selectively encapsulated inside the blue box in water whereas DASA-Bar was mostly separated out from the solution after centrifugation, and this phenomenon was confirmed by 1H and DOSY NMR and mass spectroscopies. Moreover, we found through density functional theory (DFT) optimization that the open form of DASA-Mel was more stable during the encapsulation reaction in a water medium in comparison to DASA-Bar. The calculated binding energies of encapsulated DASA-Mel and DASA-Bar are -10.2 and -9.9 kcal/mol, respectively, clearly showing that the former is more stable by 0.3 kcal. Consequently, the organic macrocycle selectively separating one kind of DASA from a mixture by encapsulation in water is reported for the first time with experimental and theoretical support in the literature.

Recent Advances in Fluorescence Light-Up Endogenous and Exogenous Carbon Monoxide Detection in Biology.

Considerable attention has been paid by the scientific community to detect toxic carbon monoxide (CO) in sub-cellular organelles like mitochondria, lysosomes, nuclei, etc. due to their generation and accumulation through numerous biological processes and their role as signal transducer, therapeutics, etc. Various methods are also available for detection of CO, but fluorescence light-up detection is considered the best due to its easy and accurate sensing capability. As of now, no review is available in the literature dedicated to fluorescent detection of only CO both in vitro and in vivo, but considering the huge amount of work reporting every year, it is necessary to have an account of all the recent significant works devoted to it. This review will give special attention to the most noteworthy development of fluorescent light-up probes for the detection of cellular and sub-cellular targetable CO starting from 2012 and emphasizing also the mechanism of action and the applications.

Linkage induced enhancement of fluorescence in metal-carbene bond directed metallacycles and metallacages.

Two new 1,4-dihydropyrrolo[3,2-b]pyrrole based aggregation induced emission (AIE)-inactive di- and tetra-imidazolium salts were employed with Ag(i) for the synthesis of a Ag-carbene bond directed metallacycle (1) and metallacage (2), respectively. Transmetalation of these complexes allowed their facile conversion to their respective Au(i)-metallacycle (3) and metallacage (4). The final assemblies exhibit linkage induced enhancement of fluorescence (LIEF). The free ligands are almost non-fluorescent (ΦF = 3.2, 3.4) in comparison to their metal-carbene counterparts (ΦF up to 32.0). Thus, without using any AIEgen, obtaining high emission efficiencies in complexes AgI-CNHC (1, 2) via linkage is a nice approach towards turn-on fluorescence.

Manipulating Metallogel Properties by Luminogens and Their Applications in Cell Imaging.

Manipulating gelation properties of the isomeric zinc-terpyridine complexes C-1 (nongelator) and C-2 (gelator) using three different luminescent dyes, viz., acridine yellow (AY), ethidium bromide (EB), and azido-boron dipyrromethene, have been described. Hybrid gels created by the combination of C-1, C-2, and above-mentioned dyes have been termed complex-luminogen mixed gels (CLMGs). Ensuing CLMGs have been thoroughly characterized by spectral, morphological, and rheological studies. Cytotoxicity measurements and imaging against breast cancer cell line MDA-MB-231 unveiled that three out of the five CLMGs can be effectively used for cell imaging. Interestingly, direct use of the metal-containing hybrid gels for live cell imaging which is a distinctive approach, has been successfully achieved with significantly encouraging results.

Anticancer Activity of Iridium(III) Complexes Based on a Pyrazole-Appended Quinoline-Based BODIPY.

A pyrazole-appended quinoline-based 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (L1, BODIPY) has been synthesized and used as a ligand for the preparation of iridium(III) complexes [Ir(phpy)2(L1)]PF6 (1; phpy = 2-phenylpyridine) and [(η5-C5Me5)Ir(L1)Cl]PF6 (2). The ligand L1 and complexes 1 and 2 have been meticulously characterized by elemental analyses and spectral studies (IR, electrospray ionization mass spectrometry, 1H and 13C NMR, UV/vis, fluorescence) and their structures explicitly authenticated by single-crystal X-ray analyses. UV/vis, fluorescence, and circular dichroism studies showed that complexes strongly bind with calf-thymus DNA and bovine serum albumin. Molecular docking studies clearly illustrated binding through DNA minor grooves via van der Waals forces and their electrostatic interaction and occurrence in the hydrophobic cavity of protein (subdomain IIA). Cytotoxicity, morphological changes, and apoptosis have been explored by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and Hoechst 33342 staining. IC50 values for complexes (1, 30 µM; 2, 50 µM) at 24 h toward the human cervical cancer cell line (HeLa) are as good as that of cisplatin (21.6 µM) under analogous conditions, and their ability to kill cancer cells lies in the order 1 > 2. Because of the inherent emissive nature of the BODIPY moiety, these are apt for intracellular visualization at low concentration and may find potential applications in cellular imaging and behave as a theranostic agent.

Influence of substituents on DNA and protein binding of cyclometalated Ir(iii) complexes and anticancer activity.

Synthesis of terpyridyl based ligands 3-([2,2':6',2''-terpyridin]-4'-yl)-7-methoxy-2-(methylthio)-quinolone, (L1); 3-([2,2':6',2''-terpyridin]-4'-yl)-6-methoxyquinolin-2(1H)-one, (L2); 3-([2,2'-:6',2''-terpyridin]-4'-yl)-6-methylquinolin-2(1H)-one (L3) and cyclometalated iridium(iii) complexes [[Ir(ppy)2L1]+PF6- (1), [Ir(ppy)2L2]+PF6- (2), [Ir(ppy)2L3]+PF6- (3) (2-phenylpyridine = Hppy)] involving these ligands has been described. The ligands L1-L3 and complexes 1-3 have been thoroughly characterized by elemental analyses, spectral studies (IR, 1H, 13C NMR, UV/vis and fluorescence) ESI-MS, and the structure of 3 has been unambiguously authenticated by single crystal X-ray analyses. UV/vis, fluorescence and circular dichroism spectroscopic studies showed rather efficient binding of 1 with CT-DNA (calf thymus DNA) and BSA (bovine serum albumin) relative to 2 and 3. Molecular docking studies unveiled binding of 1-3 with minor groove of CT-DNA via van der Waal's forces and electrostatically with the hydrophobic moiety of HSA (human serum albumin). The ligands and complexes exhibited moderate cytotoxicity towards MDA-MB-231 (breast cancer cell line) and significant influence on HeLa (cervical cancer cell line) cells. Cytotoxicity, morphological changes, and apoptosis have been followed by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide) assay, Hoechst 33342/PI (PI = propidium iodide) staining, cell cycle analysis by FACS (fluorescence activated cell sorting), and ROS (reactive oxygen species) generation by DCFH-DA (dichlorodihydrofluorescein diacetate) dye. Confocal microscopy images revealed that the drug efficiently initiates apoptosis in the cell cytosol. The IC50 values showed superior cytotoxicity of 1-3 against the HeLa cell line relative to cisplatin, and their ability to induce apoptosis is in the order 1 > 2 > 3.

Spacer length dependent architectural diversity in bis-dipyrrin copper(ii) complexes.

A series of copper(ii) complexes (1-9 and 3') derived from bis-dipyrrin ligands (L1-L9 and L3') with diverse spacer lengths [-(CH2)n-] have been described. Structural diversities in these complexes have been explicitly established by spectral and structural studies on these and a closely related nickel(ii) complex (3''). All the ligands and complexes have been thoroughly characterized by spectroscopic studies (ESI-MS, IR, 1H, 13C NMR, UV/vis) and structures of 2, 3', 3'', 6, 8 and 9 were determined by X-ray single crystal analyses. It has been unambiguously established that ligands with n ≤ 6 gave heteroleptic binuclear (1-5), while those with n ≥ 7 yielded homoleptic mononuclear (6-9) bis-dipyrrinato complexes. Spectral and structural studies revealed distorted square planar (1-5) and distorted tetrahedral geometries (6-9) about the copper(ii) centre in these complexes which has further been evidenced by EPR and electrochemical studies. Structural differences based on the odd and even number of methylene spacers in these complexes have been supported by DFT studies. A line between the syn- and anti-conformations of the complexes has been drawn on the basis of a limiting spacer length.

Anion triggered metallogels: demetalation and crystal growth inside the gel matrix and improvement in viscoelastic properties using Au-NPs.

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.

Heteroleptic arene Ru(II) dipyrrinato complexes: DNA, protein binding and anti-cancer activity against the ACHN cancer cell line.

Four organometallic complexes [(η(6)-C6H6)RuCl(pmpzdpm)], 1; [(η(6)-C6H6)RuCl(pypzdpm)], 2; [(η(6)-C10H14)RuCl(pmpzdpm)], 3 and [(η(6)-C10H14)RuCl(pypzdpm)], 4 containing 5-(2-pyrimidyl-piperazine)phenyldipyrromethene (pmpzdpm) and 5-(2-pyridylpiperazine)phenyldipyrromethene (pypzdpm) have been designed and synthesized. The complexes 1-4 have been fully characterized by elemental analyses and spectroscopic studies (ESI-MS, IR, (1)H, (13)C NMR, UV-vis). Their electrostatic/intercalative interaction with CT DNA has been investigated by UV-vis and competitive ethidium bromide displacement studies while their protein binding affinity toward bovine serum albumin (BSA) was realized by UV-vis, fluorescence, synchronous and three dimensional (3D) fluorescence studies. The interaction with DNA and protein has further been validated by in silico studies. Cellular uptake, in vitro cytotoxicity and flow cytometric analyses have been performed to determine the mode of cell death against the kidney cancer cell line ACHN. Cell cycle analysis suggested that the complexes cause cell cycle arrest in the subG1 phase and overall results indicated that the in vitro antitumor activity of 1-4 lies in the order of 3 >4 >1 >2 (IC50, 7.0 1; 8.0 2; 2.0 3; 4.0 µM,4 ).

Photochemical water oxidation by cyclometalated iridium(iii) complexes: a mechanistic insight.

The proficiency of the cyclometalated iridium complexes [(η(5)-C5Me5)IrCl(L1)] (1), [(η(5)-C5Me5)IrCl(L2)] (2) and [(η(5)-C5Me5)IrCl(L3)] (3) has been examined towards photochemical water oxidation. The involvement of Ir(iv/v) in the catalytic process has been explored via CV, UV/vis, XPS spectroscopic studies and appreciable TON relative to the theoretical value of 1 from GC.

Exquisite 1D Assemblies Arising from Rationally Designed Asymmetric Donor-Acceptor Architectures Exhibiting Aggregation-Induced Emission as a Function of Auxiliary Acceptor Strength.

One-dimensional nanostructures with aggregation-induced emission (AIE) properties have been fabricated to keep the pace with growing demand from optoelectronics applications. The compounds 2-[4-(4-methylpiperazin-1-yl)benzylidene]malononitrile (PM1), 2-{4-[4-(pyridin-2-yl)piperazin-1-yl]-benzylidene}malononitrile (PM2), and 2-{4-[4-(pyrimidin-2-yl)piperazin-1-yl]benzylidene}malononitrile (PM3) have been designed and synthesized by melding piperazine and dicyanovinylene to investigate AIE in an asymmetric donor-acceptor (D-A) construct of A'-D-π-A- topology. The synthetic route has been simplified by using phenylpiperazine as a weak donor (D), dicyanovinylene as an acceptor (A), and pyridyl/pyrimidyl groups (PM2/PM3) as auxiliary acceptors (A'). It has been established that A' plays a vital role in triggering AIE in these compounds because the same D-A construct led to aggregation-caused quenching upon replacing A' with an electron-donating ethyl group (PM1). Moreover, the effect of restricted intramolecular rotation and twisted intramolecular charge transfer on the mechanism of AIE has also been investigated. Furthermore, it has been clearly shown that the optical disparities of these A'-D-π-A architectures are a direct consequence of comparative A' strength. Single-crystal X-ray analyses provided justification for role of intermolecular interactions in aggregate morphology. Electrochemical and theoretical studies affirmed the effect of the A' strength on the overall properties of the A'-D-π-A system.

A dual-responsive "turn-on" bifunctional receptor: a chemosensor for Fe3+ and chemodosimeter for Hg2+.

Synthesis of L1-L3, their thorough characterization by spectral as well as structural studies and use in selective photochemical detection of Fe(3+) and Hg(2+) at ppb level have been described. Notably, these exhibit bifunctional behaviour toward Fe(3+) (CHEF) and Hg(2+) (chemodosimetric) which has been unequivocally established by various studies.