Pyridine appended pyrimidine bis hydrazone: Zn2+/ATP detection, bioimaging and functional properties of its dinuclear Zn(II) complex.

A pyridine functionalized pyrimidine-based system, H2P was successfully synthesized, characterized, and evaluated for its remarkable selective characteristics towards Zn2+ and ATP ions. The chemical sensing capabilities of H2P were demonstrated through absorption, fluorescence, and NMR spectroscopic techniques. The probe exhibited outstanding sensitivity when interacting with the ions, demonstrating relatively strong association constants and impressively low detection limits. The comprehensive binding mechanism of H2P with respect to Zn2+ and ATP ions was investigated using a combination of analytical methods, including Job's plot, NMR spectroscopy, mass spectrometry, and density functional theory (DFT) experiments. The interesting sensing ability of H2P for Zn2+/ATP ions was harnessed for live cell bioimaging and other diverse on-site detection purposes, including paper strips, cotton swabs, and applications involving mung bean sprouts. Further, the fluorescent probe demonstrated its effectiveness in detecting Zn2+ and ATP within live cells, indicating its significant potential in the realm of biological imaging applications. Moreover, the molecular configuration of the zinc complex (H2P-Zn2Cl4), derived from H2P, was elucidated using X-ray crystallography. This complex exhibited intriguing multifunctional attributes, encompassing its capability for detecting picric acid and for reversible acid/base sensing responses. The enhanced conducting behavior of the complex as well as its resistance properties were investigated by performing I-V characteristics and electrochemical impedance spectroscopic (EIS) experiments respectively.

Diethylaminophenol appended pyrimidine bis hydrazone for the sequential detection of Al3+ and PPi ions.

In this study, a novel easy-to-prepare diethylaminophenol appended pyrimidine bis hydrazone (HD) has been designed and developed. The probe exhibits excellent sequential sensing characteristics towards Al3+ and PPi ions. The emission studies, various spectroscopic techniques and lifetime results have been utilized to understand the binding mechanism of HD with Al3+ ions and, to discover the specificity as well as the efficacy of the probe in sensing Al3+ ions. The good association constant in addition to the lower detection limit values makes the probe effective for the detection of Al3+. The in-situ produced HD-Al3+ ensemble could consecutively detect PPi via a turn-off fluorescence response and the selectivity and sensitivity characteristics of the generated ensemble towards PPi were described based on the demetallation approach. The overall sensing property of HD was perfectly employed for constructing logic gates, real water, and tablet applications. Paper strips, as well as cotton-swab experiments, were also conducted inorder to check the practical utility of the synthesized probe.

C3-symmetric triaminoguanidine based colorimetric and fluorometric chemosensor: Sequential detection of Zn2+/PPi, its RGB performance for detection of Zn2+ ion and construction of IMPLICATION logic gate.

In this work, new ethyl(E)-2-cyano-3-(1H-pyrrol-2-yl)acrylate appended C3-symmetric star-shape triaminoguanidine based Schiff base (LH3) was designed and synthesized from simple synthons. New probe, LH3 was completely analyzed by 1H NMR, 13C NMR and mass spectrum. In the present probe LH3, effective π-conjugated ethyl(E)-2-cyano-acrylate unit was introduced on the periphery of the pyrrole-triaminoquanidine conjugates by using carefully chosen building units. The probe LH3 shows high selectivity and sensitivity towards Zn2+ ion via colorimetric and fluorometric changes. The yellowish orange color of LH3 solution turned to wine red color upon addition of Zn2+ solution, along with red shifted absorption maxima from 450 nm to 550 nm, this indicates the formation of LH3-Zn2+ species. Job's plot and mass spectrum analysis confirms the formation of 1:3 stoichiometric complex between the LH3 and Zn2+ ions. Further this ensemble shows selective detection towards PPi anion over the other anions based on displacement metal ion approach. Hence, reversible colorimetric/emission response of LH3 towards Zn2+ and PPi ions via "on-off-on" manner could allow the construction of IMPLICATION logic gate functions. The practical efficacy of the probe LH3 was established by utilization of the probe for the detection of Zn2+ ions in real water sample analysis. Further, the significant noticeable colorimetric changes of the probe LH3 upon addition of Zn2+ ion have been successfully integrated with a smartphone app RGB color value to construct a real-time analysis of Zn2+ ions.

Simple C3-symmetric triaminoguanidine-triphenylamine conjugate as an efficient colorimetric sensor for Cu(II) and fluorescent sensor for Fe(III) ions.

The design and construction of novel C3-symmetric triaminoguanidine-triphenylamine conjugate (L) has been demonstrated and it displays positive solvatochromic behaviour with an increase in solvent polarity. The probe L acts as a selective colorimetric sensor for Cu2+ ions over other metal ions. Further, it shows high selective and sensitive detection of Fe3+ ions through turn-on fluorescence response. Moreover, the detection limits for Cu2+ and Fe3+ ions were found to be within the allowable range of the World Health Organisation (30 µM). The real-time application of the probe was showed by paper strip experiments as well as detection of Fe3+ ions in pharmaceutical tablets.

Selective detection of pyrophosphate anion by zinc ensemble of C3-symmetric triaminoguanidine-pyrrole conjugate and its biosensing applications.

A new-fangled C3-symmetric triaminoguanidine-pyrrole conjugate has been constructed and utilized for sensing applications. The probe selectively detects zinc ions (Zn2+) by colorimetric as well as turn-on fluorescent manner. Further, the in-situ formed zinc ensemble displays turn-off fluorescence response towards the pyrophosphate anion (PPi) via displacement approach. Emissive off-on-off sensing characteristics of the probe has been successfully exploited to construct the INHIBIT logic gate, coding/decoding of messages and in vivo imaging of Zn2+/PPi in zebrafish larvae. Further, PPi detection characteristics of zinc ensembles were established for the sensing of PPi discharged from DNA synthesis and other biological reactions.

Star-Shaped ESIPT-Active Mechanoresponsive Luminescent AIEgen and Its On-Off-On Emissive Response to Cu2+/S2.

Design and development of multifunctional materials have drawn incredible attraction in recent years. Herein, we report the design and construction of versatile star-shaped intramolecular charge transfer (ICT)-coupled excited-state intramolecular proton transfer (ESIPT)-active mechanoresponsive and aggregation-induced emissive (AIE) luminogen triaminoguanidine-diethylaminophenol (LH3 ) conjugate from simple precursors triaminoguanidine hydrochloride and 4-(N,N-diethylamino)salicylaldehyde. Solvent-dependent dual emission in nonpolar to polar protic solvents implies the presence of ICT-coupled ESIPT features in the excited state. Aggregation-enhanced emissive feature of LH3 was established in the CH3CN/water mixture. Furthermore, this compound exhibits mechanochromic fluorescence behavior upon external grinding. Fluorescence microscopy images of pristine, crystal, and crushed crystals confirm the naked-eye mechanoresponsive characteristics of LH3 . In addition, LH3 selectively sensed a Cu2+ ion through a colorimetric and fluorescence "turn-off" route, and subsequently, the LH3 -Cu2+ ensemble could act as a selective and sensitive sensor for S2- in a "turn-on" fluorescence manner via a metal displacement approach. Reversible "turn-off-turn-on" features of LH3 with Cu2+/S2- ions were efficiently demonstrated to construct the IMPLICATION logic gate function. The Cu2+/S2--responsive sensing behavior of LH3 was established in the paper strip experiment also, which can easily be characterized by the naked eye under daylight as well as a UV lamp (λ = 365 nm).

Coumarin based hydrazone as an ICT-based fluorescence chemosensor for the detection of Cu2+ ions and the application in HeLa cells.

We have constructed a new coumarin based fluorescence probe BENZPYR with ICT character through condensation of N, N-diethylamino-3-acetyl coumarin with 2-hydrazinobenzothiazole. The absorbance and fluorescence spectral characteristics of BENZPYR revealed that the chemosensor can specifically detect for Cu2+ ions over other different metal ions and the lowest limit of detection was found in nano molar range. The turn off sensor of BENZPYR is related to chelation enhanced quenching (CHEQ) and intramolecular charge transfer (ICT) processes were serve as excellent fluorescent detection of Cu2+ ions in DMF medium. Fluorescence microscopy experiments revealed that probe BENZPYR may have application as a fluorophore to detect the Cu2+ in living cells. The simulated DFT analysis of electronic and structural properties and also UV-vis absorption spectra are in well accordance with the experimental UV-vis absorption spectra.

D-A-D Structured Bis-acylhydrazone Exhibiting Aggregation-Induced Emission, Mechanochromic Luminescence, and Al(III) Detection.

A readily accessible D-A-D triad molecule 1 was synthesized through acylhydrazone bond formation using carefully chosen building blocks. The molecule 1 exhibits emission through charge-coupled proton transfer and enhanced emission induced through aggregation and mechanochromic luminescence. Further, it detects Al(III) selectively among other cations in an efficient manner.

Cerium-Complex-Catalyzed Oxidation of Arylmethanols under Atmospheric Pressure of Dioxygen and Its Mechanism through a Side-On µ-Peroxo Dicerium(IV) Complex.

A new Ce(IV) complex [Ce{NH(CH2CH2N=CHC6H2-3,5-(tBu)2-2-O)2}(NO3)2] (1), bearing a dianionic pentadentate ligand with an N3O2 donor set, has been prepared by treating (NH4)2Ce(NO3)6 with the sodium salt of ligand L1. Complex 1 in the presence of TEMPO and 4 Å molecular sieves (MS4 A) has been found to serve as a catalyst for the oxidation of arylmethanols using dioxygen as an oxidant. We propose an oxidation mechanism based on the isolation and reactivity study of a trivalent cerium complex [Ce{NH(CH2CH2N=CHC6H2-3,5-(tBu)2-2-O)2}(NO3)(THF)] (2), its side-on µ-O2 adduct [Ce{NH(CH2CH2N=CHC6H2-3,5-(tBu)2-2-O)2}(NO3)]2(µ-η(2):η(2)-O2) (3), and the hydroxo-bridged Ce(IV) complex [Ce{NH(CH2CH2N=CHC6H2-3,5-(tBu)2-2-O)2}(NO3)]2(µ-OH)2 (4) as key intermediates during the catalytic cycle. Complex 2 was synthesized by reduction of 1 with 2,5-dimethyl-1,4-bis(trimethylsilyl)-1,4-diazacyclohexadiene. Bubbling O2 into a solution of 2 resulted in formation of the peroxo complex 3. This provides the first direct evidence for cerium-catalyzed oxidation of alcohols under an O2 atmosphere.

Dihaloborenium cations stabilized by a four-membered N-heterocyclic carbene: electron deficiency compensation by asymmetric structural changes.

The synthesis, characterization and X-ray analysis of dichloro- and dibromo-borenium cations stabilized by a 4-membered carbene are reported. The ligand's structural changes, atypical for similar systems, were caused by coordination to electron deficient fragments and its CN2P ring strain.

A phosphorus-based compartmental ligand, (S)P[N(Me)N=CH-C6H3-2-O-3-OMe]3 (LH3), enables the assembly of luminescent heterobimetallic linear {L2Zn2Ln}+ [Ln = Gd, Tb, Nd and Eu] complexes.

The sequential reaction of a phosphorus-based trishydrazone ligand, LH3 with anhydrous ZnCl2 and LnCl3·6H2O in a 2 : 2 : 1 stoichiometric ratio in the presence of triethylamine as the base leads to the formation of monocationic trinuclear complexes [L2Zn2Ln]Cl {Ln = Gd (1), Tb (2), Nd (3), Eu (4) and L = [(S)P[N(Me)N=CH-C6H3-2-O-3-OMe]3}. All the three metal ions, in each of these compounds, are arranged in a linear fashion. The two terminal Zn(II) ions are encapsulated by three imino and three phenolate oxygen atoms while the lanthanide ion remains in the centre with an all-oxygen coordination environment. Detailed photophysical measurements reveal the complete absence of antenna sensitization in all the four complexes. However, a strong emission was found for 2 and 4 when excited directly at their f-f levels.

Coordination polymers of zinc with (η6-benzenecarboxylate) chromium tricarbonyl.

Different coordination polymers were obtained by the reaction of (benzoic acid) chromium tricarbonyl with zinc acetate in the presence of various organic dipyridyl linkers. Depending on the nature of the linker either monomeric or polymeric compounds were obtained. Reactions of (benzoic acid) chromium tricarbonyl with zinc acetate and bidentate pyridine based ligands 4,4'-bipyridine (4,4'-bipy), 1,2-bis(4-pyridyl)ethane (bpe), 1,3-bis(4-pyridyl)propane (tmdp), and 2,2'dipyridylamine (DPA) afforded the novel coordination polymers [Zn[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)(4,4'-bipy)](n), [Zn[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)(bpe)](n), [Zn[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)(tmdp)}](n), and the monomeric complex [Zn[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)(DPA)]. The solid state structures of all compounds were determined by single crystal X-ray diffraction. By using 1,3-bis(4-pyridyl)propane as a linker a chiral infinite helical structure was formed in the solid state. Thermogravimetric analysis (TGA) studies showed that upon heating the carbonyl groups of the {η(6)-C(6)H(5)COO}Cr(CO)(3) anion were lost before the organic ligand sphere was thermally decomposed.

Sodium and potassium compounds of [(η(6)-benzenecarboxylate)Cr(CO)(3)] and [(η(6)-1,4-benzenedicarboxylate)Cr(CO)(3)].

Reactions of [{η(6)-C(6)H(5)COOH}Cr(CO)(3)] with sodium and potassium hydroxide resulted in the corresponding alkali metal derivatives [Na(H(2)O)(3){η(6)-C(6)H(5)COO}Cr(CO)(3)] and [K(2)(H(2)O)(CH(3)OH)(1.5)[{η(6)-C(6)H(5)COO}Cr(CO)(3)](2)]. Deprotonation of [{η(6)-p-C(6)H(4)(COOH)(2)}Cr(CO)(3)] with sodium and potassium hydroxide gave the sodium compound [{Na(H(2)O)(3)}(2){η(6)-p-C(6)H(4)(COO)(2)}Cr(CO)(3)] and the potassium compound [{K(2)(CH(3)OH)(H(2)O)(2)}{η(6)-p-C(6)H(4)(COO)(2)}Cr(CO)(3)]. All substances form two-dimensional structures in the solid state. Hydrogen bonds are observed in all sodium complexes between some carboxylate groups and coordinated water molecules. The hydrogen bonds are an essential part of the network. As a result of the higher coordination number of the potassium atoms, the polymeric networks can be constructed by direct interaction of the oxygen atoms of the carboxylic anions with the alkali metal atom. No hydrogen bonds are observed in the potassium compounds. In all compounds, except those of [Na(H(2)O)(3){η(6)-C(6)H(5)COO}Cr(CO)(3)], the alkali metal atoms form isocarbonyl bridges to the chromium atoms.

Synthesis, structure, and two-photon absorption studies of a phosphorus-based tris hydrazone ligand (S)P[N(Me)N=CH-C6H3-2-OH-4-N(CH2CH3)2]3 and its metal complexes.

A phosphorus-supported multidentate ligand (S)P[N(Me)N=CH-C(6)H(3)-2-OH-4-N(CH (2)CH(3))(2)](3) (1) has been used to prepare mononuclear complexes LM [M = Fe (2) Co (3)] and trinuclear complexes L(2)M(3) [M = Mn (4), Ni (5), Zn (6), Mg (7), Cd (8)]. In both 2 and 3 the ligand binds the metal ion in a facial coordination mode utilizing three imino nitrogen (3N) and three phenolic oxygen (3O) atoms. The molecular structures of L(2)Mn(3), L(2)Ni(3), L(2)Zn(3), L(2)Mg(3), and L(2)Cd(3) (4-8) are similar; two trihydrazone ligands are involved in coordination to hold the three metal ions in a linear fashion. Each of the trishydrazone ligands behaves as a trianionic hexadentate ligand providing three imino and three phenolic oxygen atoms for coordination to the metal ions. The coordination environment around the two terminal metal ions is similar (3N, 3O) while the central metal ion has a 6O coordination environment. Third-order non-linear optical properties of these compounds as measured by their two-photon absorption (TPA) cross section reveals that while 1 does not possess obvious TPA activity, complexes 2 (3213 GM) and 4 (3516 GM) possess a large TPA cross section at 770 nm.

Phosphorus-supported ligands for the assembly of multimetal architectures.

Modeled after boron-based scorpionate ligands, acyclic and cyclic phosphorus-containing compounds possessing reactive groups can serve as excellent precursors for the assembly of novel phosphorus-supported ligands that can coordinate multiple sites. In such ligands, the phosphorus atom does not have any role in coordination but is used as a structural support to assemble one or more coordination platforms. In this Account, we describe the utility of inorganic heterocyclic rings such as cyclophosphazenes and carbophosphazenes as well as acyclic phosphorus-containing compounds such as (S)PCl(3), RP(O)Cl(2), and R(2)P(O)Cl for building such multisite coordination platforms. We can modulate the number and orientation of such coordination platforms through the choice of the phosphorus-containing precursor. This methodology is quite general and modular and allows the creation of well-defined libraries of multisite coordination ligands. Phosphorus-supported pyrazolyl ligands are quite useful for building multimetallic architectures. Some of these ligands are prone to P-N bond hydrolysis upon metalation, but we have exploited the P-N bond sensitivity to generate hydrolyzed ligands in situ, which are useful to build multimetal assemblies. In addition, the intimate relationship between small molecule cyclophosphazenes and the corresponding pendant cyclophosphazene-containing polymer systems facilitated our design of polymer-supported catalysts for phosphate ester hydrolysis, plasmid DNA modification, and C-C bond formation reactions. Phosphorus hydrazides containing reactive amine groups are ideal precursors for integration into more complex ligand systems. The ligand (S)P[N(Me)N=CH-C(6)H(4)-2-OH](3) (LH(3)) contains six coordination sites, and its coordination response depends upon the oxidation state of the metal ion employed. LH(3) reacts with divalent transition metal ions to afford neutral trimetallic derivatives L(2)M(3), where the three metal ions are arranged in a perfectly linear manner in many cases. Incorporating an additional methoxy group into LH(3) affords the ligand (S)P[N(Me)N=CH-C(6)H(3)-2-OH-3-OMe](3) (L'H(3)), which contains nine coordination sites: three imino nitrogen atoms, three phenolate oxygen atoms, and three methoxy oxygen atoms. The reaction of L'H(3) with transition metal salts in 1:1 ratio leads to the in situ formation of a metalloligand (L'M), which on further treatment with lanthanide salts gives heterobimetallic trinuclear cationic complexes [L'(2)M(2)Ln](+) containing a M-Ln-M linear array (M = transition metal ion in a +2 oxidation state). Many of these 3d-4f compounds behave as single-molecule magnets at low temperatures. Although challenges remain in the development of synthetic methods and in the architectural control of the coordination platforms, we see opportunities for further research into coordination platforms supported by main group elements such as phosphorus. As we have shown in this Account, one potential disadvantage, sensitivity of P-N bonds to hydrolysis, can be used successfully to build larger assemblies.