Fluoranthene-terminated terpyridine ensemble for fluorescence light up and ratiometric chemical sensor for multi toxic metals.

A novel π-electron rich fluoranthene embellished with a phenyl spacer and coupled with terpyridine (TS1) was developed through Diels-Alder reaction. Single crystal X-ray structure evidences the variations in dihedral angles between the fluoranthene and the phenyl unit responsible for development of non-coplanar interactions and stabilized by a wave-like molecular packing in the crystal lattice with weak π-π interaction of 4.125 Å. The peripheral terpyridine of TS1 endows an efficient binding with multiple metal ions by colorimetric and fluorometric methods. TS1 exhibits a ratiometric fluorescence response from sky blue to yellow colour upon the addition of Zn2+ ions with a limit of detection (LOD) of 0.05 ppm. The other metal ions such as Cu2+, Co2+ and Fe2+ demonstrate fluorescence quenching behaviour with LODs of 0.1, 0.3 and 0.7 ppm, respectively. The intramolecular charge transfer (ICT) shows the variation in TS1 emission behaviour upon metal ions interaction and quantitatively discriminates the metal ion concentrations. TS1 conferred a visual colorimetric change from colourless to magenta, enabling naked-eye detection of Fe2+ and showing clear discrimination between Fe2+ and Fe3+ ions for the real-time water samples. Furthermore, we have investigated the effect of TS1 in Zebrafish larvae/embryos and cytotoxicity in human urinary tract transitional cell carcinoma cells (UM-UC-3).

Self-Assembled Manganese(I)-Based Selenolato-Bridged Tetranuclear Metallorectangles: Host-Guest Interaction, Anticancer, and CO-Releasing Studies.

Supramolecular one-step self-assembly of dimanganese decacarbonyl, diaryl diselenide, and linear dipyridyl ligands (L = pyrazine (pz), 4,4'-bipyridine (bpy), and trans-1,2-bis(4-pyridyl)ethylene (bpe)) has resulted in the formation of selenolato-bridged manganese(I)-based metallorectangles. The synthesis of tetranuclear Mn(I)-based metallorectangles [{(CO)3Mn(µ-SeR)2Mn(CO)3}2(µ-L)2] (1-6) was facilitated by the oxidative addition of diaryl diselenide to dimanganese decacarbonyl with the simultaneous coordination of linear bidentate pyridyl linker in an orthogonal fashion. Formation of metallorectangles 1-6 was ascertained using IR, UV-vis, NMR spectroscopic techniques, and elemental analyses. The molecular mass of compounds 2, 4, and 6 were determined by ESI-mass spectrometry. Solid-state structural elucidation of 2, 3, and 6 by single-crystal X-ray diffraction methods revealed a rectangular framework wherein selenolato-bridges and pyridyl ligands define the shorter and longer edges, respectively. Also, the guest binding capability of metallorectangles 3 and 5 with different aromatic guests was studied using UV-vis absorption and emission spectrophotometric titration methods that affirmed strong host-guest binding interactions. The formation of the host-guest complex between metallorectangle 3 and pyrene has been explicitly corroborated by the single-crystal X-ray structure of 3•pyrene. Moreover, select metallorectangles 1-4 and 6 were studied to explore their anticancer activity, while CO-releasing ability of metallorectangle 2 was further appraised using equine heart myoglobin assay.

Amide-Functionalized Chalcogen-Bridged Flexible Tetranuclear Rhenacycles: Synthesis, Characterization, Solvent Effect on the Structure, and Guest Binding.

The synthesis of flexible rhenium(I)-based amide-functionalized chalcogen-bridged tetranuclear metallacycles of general formula [{(CO)3Re(µ-ER)2Re(CO)3}2(µ-L)2] (1-8) was achieved by treating rhenium carbonyl with dialkyl/diaryl chalcogenide (RE-ER; E = S and Se) in the presence of ditopic flexible or semiflexible pyridyl ligand with amide functionality (L = N,N'-bis(4-pyridylcarboxamide)-1,2-ethane (bpce) and N,N'-bis(4-(4-pyridylcarboxamide)phenyl)methane (bpcpm)). Compounds 1-8 were formed by multicomponent self-assembly under one-pot reaction conditions via oxidative addition of dialkyl/diaryl chalcogenide to rhenium carbonyl with pyridyl ligands. The resultant metallacyclophanes were characterized using elemental analyses, infrared, ultraviolet-visible, and NMR spectroscopic techniques. Metallacyclophanes 1-3 and 7 were structurally characterized by single-crystal X-ray diffraction methods. The solvent-induced structural change of flexible tetranuclear metallacyclophane 2 was demonstrated by crystallizing 2 in dichloroethane and dimethylformamide. Molecular recognition capabilities of 2 and 7 were studied with few aromatic compounds containing ethereal linkages.

Self-assembly of oxamidato bridged ester functionalised dirhenium metallastirrups: synthesis, characterisation and cytotoxicity studies.

A new set of ester functionalised Re(i)-based oxamidato bridged neutral dinuclear metallacycles were synthesised by self-assembly of four components from three building blocks in a facile one-pot reaction via an orthogonal bonding approach. Oxidative addition of oxamide ligands (H2L = N,N'-diphenyloxamide, and N,N'-dibenzyloxamide) to rhenium carbonyl (Re2(CO)10) in the presence of semi-rigid and flexible ditopic pyridyl ligands (L' = o-phenylene diisonicotinate (pdi), ethane diyl di-4-pyridine carboxylate (etdp) and 1,4-butane diyl di-4-pyridine carboxylate (budp)) having ester functionality afforded neutral dirhenium metallacycles of the general formula [(CO)3Re(µ-L)(µ-L')Re(CO)3] (1-5) under solvothermal reaction conditions. The metallacyclic compounds were characterised using elemental analyses, IR, UV-vis and NMR spectroscopic techniques. Structural analyses of 2-5 by single crystal X-ray diffraction methods revealed a stirrup like molecular framework in which two fac-Re(CO)3 units are bridged together by dissymmetrical NO∩ON bis-chelation of oxamide ligands (as a pedestal of stirrups) and further connected by a flexible ditopic tecton (as an arched anchor of stirrups) in an orthogonal fashion. The cytotoxicity activities of dirhenium metallacycles 1-5 were studied in vitro against three different cancer cell lines and normal cells.

Self-assembly of Thiolato-Bridged Manganese(I)-Based Metallarectangles: One-pot Synthesis and Structural Characterization.

A new series of thiolato-bridged manganese(I)-based supramolecular rectangles have been achieved by three-precursor self-assembly of Mn2(CO)10, diaryl disulfides (RSSR), and linear ditopic azine ligands (L) [L = pyrazine (pz), 4,4'-bipyridine (bpy), and trans-1,2-bis(4-pyridyl)ethylene (bpe)] using a one-pot synthetic strategy. Oxidative addition of RSSR (diphenyl disulfide and p-tolyl disulfide) to manganese decacarbonyl in the presence of rigid bidentate ligands (L) afforded metallarectangles of the general formula [{(CO)3Mn(µ-SR)2Mn(CO)3}2(µ-L)2] (1-6). Compounds 1-6 were characterized using elemental analyses and NMR, IR, and UV-vis absorption spectroscopic techniques. The molecular structures of metallarectangles 1, 3, and 5 were elucidated by single-crystal X-ray diffraction methods. The guest binding ability of 3 and 5 has been investigated with two aromatic guests using electronic absorption and fluorescence emission spectroscopy, and the results revealed a strong binding interaction between host-guest species.