Design and Synthesis of Lead(II)-Based Electrocatalysts for Oxygen Evolution Reaction.

A well-organized worldwide effort in providing remedies to sustainable clean energy generation and storage has focused on the strategic design and development of stable and efficient earth-abundant metal (Fe, Co, Ni, Pb, etc.)-based electrocatalysts for the oxygen evolution reaction (OER). Unfortunately, examples of Pb-based catalysts for such a process are rare. In this work, based on the dual-linker strategy, we have designed and synthesized two new two-dimensional (2D) coordination polymers of Pb with the hcb topology, [Pb2(tpbn)(adc)2]·4H2O·0.5CH3OH}n (CP1) and {[Pb2(tpbn)(fum)2]·7H2O}n (CP2), in excellent yields by the room-temperature self-assembly of Pb(OAc)2, tpbn, and H2adc or H2fum (where tpbn = N,N',N‴,N‴'-tetrakis-(2-pyridylmethyl)-1,4-diaminobutane, H2adc = acetylene dicarboxylic acid, and H2fum = fumaric acid). In addition to determining their X-ray single crystal structures, the phase purity and thermal stability were established by powder X-ray diffraction and thermogravimetric analysis, respectively. Furthermore, these were also characterized by the microscopic techniques (SEM/EDX and TEM/HRTEM). For their conductive and highly stable nature in alkaline medium, both CP1 and CP2 were tested for their suitability in the OER process. Interestingly, with a subtle change from adc in CP1 to fumarate in CP2 as the dicarboxylate linker, the latter performed much better than the former and displayed an excellent electrochemical stability in basic medium. Remarkably, CP2 has one of the lowest Tafel values (35 mV dec-1) and a low overpotential value (140 mV vs RHE) in 0.5 M KOH compared to those reported for any materials. Such a comparative study with CP1 and CP2, which are the simplest CPs and made with green-chemistry protocols for an easy making in large quantities, provides an outlook to developing the next-generation Pb-based electrocatalysts.

A Primary Amide-Functionalized Heterogeneous Catalyst for the Synthesis of Coumarin-3-carboxylic Acids via a Tandem Reaction.

A crystalline primary amide-based bifunctional heterogeneous catalyst, {[Cd2(2-BPXG)(Fum)2(H2O)2]·2H2O}n (1) (where, 2-BPXG = 2,2'-((1,4-phenylenebis(methylene))bis((pyridin-2-ylmethyl)azanediyl)) diacetamide and Fum = fumarate), has been developed for the one-pot synthesis of a series of potentially biologically active coumarin-3-carboxylic acids at room temperature via a Knoevenagel-intramolecular cyclization tandem reaction. Catalyst 1 is prepared at room temperature from a one-pot self-assembly process in 81% yield and high purity within a few hours and has a ladder-like polymeric architecture based on single-crystal X-ray diffraction. Additional characterization of 1 includes elemental analysis, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. Based on the optimized conditions, it is determined that 1 is highly efficient (conditions: 2 mol % catalyst, 3 h, and 26-28 °C in methanol) for this reaction. Its recyclability up to five cycles without significant loss of activity and structural integrity is also demonstrated. Using both electron-donating and electron-withdrawing substituents on the salicylaldehyde substrate, seven different derivatives of coumarin-3-carboxylic acid were made. Additionally, the monoamine oxidase (MAO) inhibitor, coumarin-3-phenylcarboxamide, has also been synthesized from coumarin-3-carboxylic acid obtained in the catalysis process. A detailed mechanism of action is also provided.

Design and Development of a Heterogeneous Catalyst for the Michael Addition of Malononitrile to 2-Enoylpyridines: Influence of the Primary Amide Decorated Framework on Catalytic Activity and Selectivity.

For the Michael addition of malononitrile to 2-enoylpyridines, we report the first heterogeneous catalyst, {[Zn2(2-bpbg)(fum)2]·4H2O·EtOH}n (1) (where 2-bpbg = N,N'-bis(2-pyridylmethyl)-1,4-diaminobutane-N,N'-diacetamide and where fum = fumarate), which is decorated with primary amide side arms. It is prepared from the self-assembly of starting materials in methanol at room temperature (27 °C). Using 3 mol % of 1, greater than 99% conversion of substrates to the desired product is achieved within 1 h at 27 °C. Moreover, the catalyst is recyclable up to five consecutive cycles without significant loss of activity and structural integrity. In order to show the uniqueness of 1, the reaction under the same conditions was catalyzed by a fully pyridyl-based (i.e., having no primary amide group) and isostructural analogue, {[Zn2(tpbn)(fum)2]·6H2O}n (2) (where tpbn = N',N',N″,N''-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine), but resulting only in 7% conversion. This demonstrates the selective catalytic activity of 1 over 2 due to the presence of the primary amide side arms, where it acts as a bifunctional catalyst through the excellent hydrogen bond donating (HBD) ability in this reaction. For providing an insight into its mechanism of action involving a cyclic seven-membered hydrogen bonding motif, the reaction was performed with freshly synthesized (E)-chalcone, 3-enoylpyridine, and 4-enoylpyridine instead of 2-enoylpyridine under the same conditions. In the case of (E)-chalcone no product formation was observed, whereas for 3-enoylpyridine and 4-enoylpyridine the conversions were only 29% and 25%, respectively. Both 1 and 2 were fully characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and single-crystal and powder X-ray diffraction.

Regeneration, degradation, and toxicity effect of MOFs: Opportunities and challenges.

Metal organic frameworks (MOFs) have been investigated extensively for separation, storage, catalysis, and sensing applications. Nonetheless, problems associated with their toxicity, recycling/reuse/regeneration, and degradation have yet to be addressed as one criterion to satisfy their commercialization. Here, the challenges associated with MOF-based technology have been explored to further expand their practical utility in various applications. We start a brief description of challenges associated with MOF-based technology followed by a critical evaluation of toxicity and need of technical options for regeneration of MOFs. Importantly, diverse techniques/process for reuse and regeneration of MOFs like activation of MOFs by heat, vacuum, solvent exchange, supercritical carbon dioxide (SCCO2) and other miscellaneous options have been discussed with recent examples. Afterward, we also present an economical aspect and future perspectives of MOFs for real world applications. All in all, we aimed to present opportunities and critical review of the current status of MOF technology with respect to their recycling/reuse/regeneration to consider their environmental impact.

Can Remote N-Heterocyclic Carbenes Coordinate with Main Group Elements? Synthesis, Structure, and Quantum Chemical Analysis of N+ -Centered Complexes.

Remote N-heterocyclic carbenes (rNHCs), such as N-methyl-4-pyridylidene, are known to form coordination complexes with TMs. Herein, it is established that rNHCs can also coordinate to the N+ centre. Synthesis of some novel divalent NI complexes with the general formula (rNHC)→N+ ←(NHC) and (rNHC)→N+ ←(rNHC) was achieved, and X-ray diffraction studies supported the coordination bond character between the rNHCs and the N+ centre. Quantum chemical analysis established the presence of divalent NI character at the central nitrogen in these systems.

Correction: An unprecedented tandem synthesis of fluorescent coumarin-fused pyrimidines via copper-catalyzed cross-dehydrogenative C(sp3)-N bond coupling.

Correction for 'An unprecedented tandem synthesis of fluorescent coumarin-fused pyrimidines via copper-catalyzed cross-dehydrogenative C(sp3)-N bond coupling' by Santosh Kumari et al., Org. Biomol. Chem., 2018, 16, 3220-3228.

An unprecedented tandem synthesis of fluorescent coumarin-fused pyrimidines via copper-catalyzed cross-dehydrogenative C(sp3)-N bond coupling.

An efficient, one-pot Cu-catalyzed tandem synthesis of fluorescent 1-benzyl-2-phenyl-1,2-dihydro-5H-chromeno[4,3-d]pyrimidin-5-ones from 4-chloro-3-formylcoumarin and benzylamines was developed by in situ intramolecular cross-dehydrogenative C(sp3)-N bond formation in moderate-to-good yields under ligand-free ambient conditions. This synthesis was easily scalable, and the generality of the substrates was established. These coumarin-fused pyrimidines exhibited interesting photo-physical properties and high quantum yields, and would be potential candidates for facilitating suitable studies in medicinal chemistry and materials science.

Design, Synthesis, and Structural Analysis of Divalent N(I) Compounds and Identification of a New Electron-Donating Ligand.

The dative-bond representation (L→E) in compounds with main group elements (E) has triggered extensive debate in the recent past. The scope and limits of this nonclassical coordination bond warrant comprehensive exploration. Particularly compounds with (L→N←L')(+) arrangement are of special interest because of their therapeutic importance. This work reports the design and synthesis of novel chemical species with the general structural formula (L→N←L')(+) carrying the unusual ligand cyclohexa-2,5-diene-4-(diaminomethynyl)-1-ylidene. Four species belonging to the (L→N←L')(+) class carrying this unconventional ligand were synthesized. Quantum chemical and X-ray diffraction analyses showed that the electronic and geometric parameters are consistent with those of already reported divalent N(I) compounds. The molecular orbital analysis, geometric parameters, and spectral data clearly support the L→N and N←L' interactions in these species. The newly identified ligand has the properties of a reactive carbene and high nucleophilicity.

Ruthenium(II)-Catalyzed Regioselective Ortho Amidation of Imidazo Heterocycles with Isocyanates.

Direct ortho amidation at the phenyl ring of 2-phenylimidazo heterocycles with aryl isocyanates has been achieved via a chelation-assisted cationic ruthenium(II) complex catalyzed mechanism. The methodology provides a straightforward, high-yielding regioselective approach toward the synthesis of an array of ortho-amidated phenylimidazo heterocycles without prior activation of C(sp2)-H. This also reports the first method for coupling of aryl isocyanates with the imidazo[1,2-a]pyridine system via a pentacyclometalated intermediate. The methodology is found to be easily scalable and could be applied toward the selective ortho amidation of 2-heteroarylimidazo[1,2-a]pyridine frameworks.

Azine-Hydrazone Tautomerism of Guanylhydrazones: Evidence for the Preference Toward the Azine Tautomer.

Guanylhydrazones have been known for a long time and have wide applications in organic synthesis, medicinal chemistry, and material science; however, little attention has been paid toward their electronic and structural properties. Quantum chemical analysis on several therapeutically important guanylhydrazones indicated that all of them prefer the azine tautomeric state (by about 3-12 kcal/mol). A set of simple and conjugated azines were designed using quantum chemical methods, whose tautomeric preference toward the azine tautomer is in the range of 3-8 kcal/mol. Twenty new azines were synthesized and isolated in their neutral state. Variable temperature NMR study suggests existence of the azine tautomer even at higher temperatures with no traces of the hydrazone tautomer. The crystal structures of two representative compounds confirmed that the title compounds prefer to exist in their azine tautomeric form.

New conformational polymorph of hydrochlorothiazide with improved solubility.

CONTEXT: To characterize a new conformation of hydrochlorothiazide (HCT) with better solubility and establishing its relationship with previously reported form I, obtained during attempted crystallization experiments. OBJECTIVE: The aim of present investigation is to unveil a new conformational polymorph (form IA) having a higher solubility compared to commercially available form I. MATERIALS AND METHODS: New form (IA) was obtained from slow evaporation as well as by solvent-antisolvent method and was then characterized by DSC, FTIR, PXRD and SCXRD. Equilibrium solubility profile shows that it is more soluble than form I. RESULTS: Appearance of phase transition endotherm at 215.87 °C in DSC spectra indicated the existence of new polymorph which was further confirmed by FTIR and PXRD. Single crystal study showed significant difference in various bond angles and torsion angles of the two forms. The solubility exhibited by form IA was (938 µg/mL) compared to form I (791 µg/mL) in water. DISCUSSION: Complete structural analysis and molecular arrangements in the unit cell along with the DSC and FTIR data confirm the existence of new conformer of HCT. CONCLUSION: This study reveals the existence of a new conformational polymorph of HCT molecule having higher solubility could prove to be promising in pre-formulation.

Characterization and evaluation of multi-component crystals of hydrochlorothiazide.

PURPOSE: The present work aims at improving the physicochemical properties of hydrochlorothiazide, a poorly water soluble antihypertensive drug by preparing its multi-component crystals with nicotinic acid (HCT-NA) and 2-picolinic acid (HCT-PIC). METHODS: The crystals prepared by solution crystallization were investigated by thermoanalytical techniques. The crystal structures of HCT-NA (1) and HCT-PIC (2) were determined by the single crystal X-ray diffraction and were assessed for their aqueous solubility, antihypertensive activity and acute toxicity in rats. RESULTS: Both 1 and 2 crystallized in the orthorhombic space group P212121 and formation of salts were confirmed. The solubility profiles of 1 and 2 in basic media showed a maximum release of 2.5 mg/ml and 1.9 mg/ml, respectively, in comparison to the drug (0.82 mg/ml). The in-vivo antihypertensive activity of 1 in deoxycorticosterone acetate salt induced hypertensive rats showed 1.5 fold improvement. No increase in the signs of toxicity were revealed in rats during the acute toxicity studies even at doses of 2,000 mg/kg by body weight in comparison to the free drug. Histopathological findings supported the safety of these multi-component crystals. CONCLUSIONS: The new solid phases exhibit potential to be explored for the oral drug delivery of HCT with improved solubility and therapeutic outcome.

One-shot photochemical synthesis of 5-(thiophen-3-yl)pyrano[2,3-c]chromen-2(3H)-ones from 3-propynyloxy-chromenones: a case of an intramolecular Paterno-Buchi reaction.

5-(Thiophen-3-yl)pyrano[2,3-c]chromen-2(3H)-ones (2), angular tricyclic compounds, were synthesized in significantly high yields through the photoinduced intramolecular coupling of the acetylenic group with the carbonyl centre in 3-(prop-2-ynyloxy)-2-(thiophen-3-yl)-4H-chromen-4-ones (1). This photoreaction is a case of an intramolecular Paterno-Buchi reaction and is unprecedented in 3-propynyloxy-chromenones. The structure of 2 has been determined by spectroscopic (FTIR, NMR and mass) and single crystal X-ray crystallographic studies.

Effect of the flexible chain length of a dimetal subunit on the formation of 1D coordination polymers to molecular rectangles.

Utilizing the angular and rigid furan dicarboxylate (fdc2-) ion, a new series of four (1-4) metal-organic coordination networks (MOCNs) is synthesized in good yields through a one-pot self-assembly reaction in methanol under ambient conditions to demonstrate the effect of Cu2 dimetal subunits, connected by flexible polypyridyl bis(tridentate) ancillary ligands, tpxn, where x refers to the number of methylene groups connecting the alkyl nitrogen atoms in the ancillary ligands and is equal to 2, 4, 6, and 7. The solid-state molecular structures of 1-4 are determined by single-crystal X-ray diffraction. A change in the dimensionality of the resultant MOCN is observed from a 1D coordination polymer (CP) for 1, 2, and 3 to a molecular rectangle for 4. Furthermore, each unit of 4 contains one NaClO4. Using electrospray ionization (ESI) mass spectrometry, their structural integrity in solution and their purity of existence as a single product are confirmed. Further characterization of 1-4 by FTIR and UV-vis (in solution and solid-state) spectroscopy, and FESEM and TEM is also reported. The presence of unsaturated metal centers in 1-4 provided an opportunity to compare their Lewis acid catalytic activities for the Knoevenagel condensation reaction of malononitrile with various aldehydes.

Deciphering supramolecular isomerization in coordination polymers: connected molecular squares vs. fused hexagons.

The self-assembly of Mn(ii), bis(tridentate) ligands and bent dicarboxylate linkers under ambient conditions has been exploited to generate a series of 1D coordination polymers in good yields. For a set of seven compounds, structural isomerization of these architectures is demonstrated through the variation of length and nature of the spacer between the tridentate capping sites of the bis(tridentate) ligands, such as tpbn (N,N',N'',N'''-tetrakis-(2-pyridylmethyl)-1,4-diaminobutane), tphxn (N,N',N'',N'''-tetrakis-(2-pyridylmethyl)-1,6-diaminohexane), and tpxn (N,N',N'',N'''-tetrakis-(2-pyridylmethyl)-xylylamine) or by varying the bent dicarboxylate linker 4,4'-(dimethylsilanediyl)bis-benzoic acid (H2L1) or 4,4'-oxybis-benzoic acid (H2L2). These compounds have been structurally characterized by single-crystal and powder X-ray diffraction, FTIR, and thermogravimetric and elemental analyses. This study reveals that the supramolecular structural variation can be precisely controlled either by a judicious selection of reaction conditions or linker/ligand combinations. For example, the self-assembly of Mn(ii), tpbn and H2L1 in DMF/EtOH/water affords a mixture of products (1 and 1a) while changing the solvent combination to EtOH/water results in the generation of a single isomer (1a) in a highly selective manner. On the other hand, for the Mn(ii)-tphxn system, different structural isomers have been isolated by varying the dicarboxylates, H2L1 and H2L2 (2vs.5). Similarly, for the Mn(ii)-H2L2 system, a variation in the spacer chain length of bis(tridentate) ligands, tpbn and tphxn resulted in the formation of different structural isomers (4vs.5).

Modulation of hydrophilicity inside the cavity of molecular rectangles self-assembled under ambient conditions.

Three novel molecular rectangles of tetranuclear Cu(ii) with a variation in the flexible methylene chain length on the two opposite sides have been synthesized from a one pot self-assembly reaction in a methanol-water mixture under ambient conditions. Their solid state molecular structures are determined by single crystal X-ray diffractometry, while their structural integrity in the solution state is confirmed by electrospray mass spectrometry. With such a subtle variation, modulation of hydrophilicity inside the cavity of these molecular rectangles is achieved as evident from the water and methanol vapor sorption studies.

Steric Effect of a Capping Ligand on the Formation of Supramolecular Coordination Networks of Ni(II): Solid-State Entrapment of Cyclic Water Dimer.

Supramolecular dimer of water is the simplest of the small water clusters [(H2O) n , n = 2-10]. During the course of our work on supramolecular coordination networks of three-component systems (divalent metal ion, tridentate capping ligand, and ditopic carboxylate linker), a cyclic water dimer is found to be entrapped in the network of [Ni2(6-Mebpta)2(adc)2]·2H2O (1) (6-Mebpta = 2-methyl-N-((6-methylpyridin-2-yl)methyl)-N-(pyridin-2-ylmethyl)propan-2-amine and adc = acetylenedicarboxylate). Based on the single-crystal structure of 1, the water dimer plays an important role in connecting the bis(adc) bridged dinickel synthons to form a one-dimensional (1D) supramolecular network. To emphasize the role of 6-Mebpta in the judicious choice of components for 1, one simple modification to it by having another methyl group in the second pendant pyridyl group to make 6,6'-Me2bpta (2-methyl-N,N-bis((6-methylpyridin-2-yl)methyl)propan-2-amine) did not allow the formation of any water cluster in [Ni(6,6'-Me2bpta)(adc)(H2O)]·H2O (2), where a different coordination environment around Ni(II) is also observed. Further quantification of the difference in supramolecular interactions observed in 1 and 2 has been assessed by Hirshfeld surface analysis. Both 1 and 2 are obtained in good yields at room temperature (methanol as solvent) and are further characterized by elemental analysis, Fourier transform infrared (FTIR) and Raman spectroscopy, powder X-ray diffraction, and thermogravimetric analysis.

Effecting structural diversity in a series of Co(II)-organic frameworks by the interplay between rigidity of a dicarboxylate and flexibility of bis(tridentate) spanning ligands.

In a one-pot self-assembly reaction of Co(OAc)2·4H2O, thiophene-2,5-dicarboxylic acid (H2tdc) and four different bis(tridentate) polypyridyl spanning ligands under ambient conditions, a series of structurally diverse metal-organic frameworks has been synthesised and characterized by single crystal X-ray diffraction: {[Co2(tdc)2(tpbn)(H2O)2]·solvent}n (solvent = 2H2O, 1; solvent = 2CH3OH, 2H2O, 1a), {[Co2(tdc)2(tphn)]·solvent}n (solvent = H2O, 2; solvent = CH3OH, 2.5H2O, 2a), {[Co2(tdc)2(tpchn)(H2O)2]·solvent}n (solvent = 5H2O, 3; solvent = C2H5OH, 2H2O, 3a), and {[Co2(tdc)2(tpxn)]·solvent}n (solvent = 6H2O, 4; when no solvent, 4a), where tpbn (N,N',N'',N'''-tetrakis(2-pyridylmethyl)-1,4-diaminobutane), tphn = N,N',N'',N'''-tetrakis(2-pyridylmethyl)-1,6-diaminohexane, tpchn = N,N'-(cyclohexane-1,4-diylbis(methylene))bis(1-(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine) and tpxn = N,N'-(1,4-phenylenebis(methylene))bis(1-(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine). There is a profound effect of the nature of spacer between the alkyl nitrogens in the spanning ligands (flexible vs. semiflexible) on the molecular structures of 1a-4a. The notable differences are (a) the binding mode of the tridentate part of polypyridyl ligands to the Co(ii) center is facial in 1a, 3a and 4a but meridional in 2a, (b) the Co(ii) centers in 1a-3a are hexacoordinated (with a coordinated water in 1a and 3a) but are pentacoordinated in 4a, and (c) the binding mode of tdc linker is bis(monodentate) in 1a, 3a and 4a but chelated in one end and monodentate in the other end in 2a. Thus, the overall framework structure of 1a, 2a, 3a and 4a is cis-decalin type 2D polymer, ladder-shaped 1D polymer, hexagonal 2D net and cis-decalin type 2D polymer, respectively. Their thermal stabilities have been established by thermogravimetric analysis (TGA). The presence of an unsaturated metal center in 4 has provided us an opportunity for its use as an efficient Lewis acid catalyst for the Knoevenagel condensation reaction of malononitrile with various aldehydes (100% conversion in 60 minutes with 2 mol% catalyst in methanol).

Novel primary amide-based cationic metal complexes: green synthesis, crystal structures, Hirshfeld surface analysis and solvent-free cyanosilylation reaction.

A new symmetrical and flexible primary amide functionalized ligand, 2,2'-(ethane-1,2-diylbis((pyridin-2-ylmethyl)azanediyl))diacetamide (2-BPEG), has been synthesized and structurally characterized. Using this multidentate ligand, four novel metal complexes, namely [Cu(2-BPEG)](ClO4)2·0.5H2O (1), [Zn(2-BPEG)](ClO4)2 (2), [Zn(2-BPEG)](ZnCl4)·H2O (3) and [Cd(2-BPEG)(H2O)](ClO4)2·H2O (4), have been synthesized under ambient conditions and characterized by elemental, spectroscopic and thermal analysis, and single and powder X-ray diffraction. Complexes 1-3 are hexacoordinated with an N4O2 donor set (provided by the hexadentate 2-BPEG ligand), while complex 4 is heptacoordinated with an additional coordinated water molecule. In all cases, the 2-BPEG ligand acts as a hexadentate ligand. A change in the starting metal salt has resulted in the formation of 2 and 3 with different tetrahedral anions, ClO4- and ZnCl4-, respectively. This has provided an opportunity to showcase anion-directed supramolecular networks for these compounds. Compounds 1, 2 and 4 with perchlorate anions show similar and comparable intermolecular interactions in their 3D networks. On the other hand, the supramolecular self-assembly of 3 is dominated by a variety of intermolecular interactions such as C-HCl, N-HCl, O-HCl and C-HO due to the presence of a tetrachlorozincate(ii) ion. Moreover, the role of weak intermolecular interactions in the crystal packing has been analysed and quantified using Hirshfeld surface analysis. Furthermore, compound 4 exhibiting an open Lewis acid site has been found to be a very efficient and recyclable heterogeneous catalyst for the solvent-free cyanosilylation of various aldehydes with trimethylsilyl cyanide (TMSCN) producing the corresponding trimethylsilyl ether in high yields.

Luminescent Lanthanide-Based Probes for the Detection of Nitroaromatic Compounds in Water.

A new mixed pyridyl-carboxylate ligand with two picolinate chromophores and a flexible linear spacer, potassium 2,2'-(butane-1,4-diylbis((pyridin-2-ylmethyl)azanediyl))diacetate (K2bpbd), which is obtained in high yield and spectroscopically characterized, has been utilized to make new lanthanide complexes, namely, [Ln(bpbd) (H2O)2(NO3)]·xH2O, where Ln = Tb (1) and x = 6, Ln = Sm (2) and x = 7, and Ln = Dy (3) and x = 7. These complexes have been extensively characterized by various spectroscopic techniques (UV-vis and Fourier transform infrared spectroscopy), elemental analyses, thermogravimetric analysis, field emission scanning electron microscopy, and powder X-ray diffraction. These show very intense characteristic luminescence features that confirm the antenna effect of the ligand on the metal center. These complexes have been utilized for the detection of various nitroaromatic compounds. Among these three complexes, 1 is found to be the best for the selective sensing of 2,4,6-trinitrophenol in water with a detection limit of (0.35 ± 0.05) ppm. Its Stern-Volmer constant, K SV [(5.48 ± 0.1) × 104 M-1], is one of the highest among similar sensors reported so far.