Sunil Varughese

Non-covalent routes to tune the optical properties of molecular materials

Switching and tuning solid state luminescence properties of molecular materials by modulating molecular packing through non-covalent routes is an attractive prospect. This strategy further makes it feasible to expand the utility of molecules of interest by obtaining a large array of solids—polymorphs, solvates, amorphous phase, nano/micro-crystals and as multi-component systems—with distinct fluorophore arrangement and hence emission characteristics. Because non-covalent interactions that determine the fluorophore arrangements in polymorphs or supramolecular complexes are weak and flexible, their making and breaking become more realistic under ambient conditions, thus having potential to achieve reversible transformations and hence external-stimuli-responsive and switchable molecular fluorescent materials. Recent advances in this context are highlighted in this review with the aid of illustrative examples and further emphasize the scope and relevance of interdisciplinary and multitechnique approaches to unravel the structure–optical property relationships and also to augment the foundations of factual knowledge.

Heteroatom induced contrasting effects on the stimuli responsive properties of anthracene based donor–π–acceptor fluorophores

Two donor–π–acceptor type fluorophores consisting of anthracene as the donor and benzoxazole (ABO) or benzothiazole (ABT) as the acceptor are synthesised. Both fluorophores exhibit excellent solid state luminescence, and respond to external stimuli such as mechanical force (mechanochromism) and protons (acidochromism). Though the differences between the two molecules are marginal, their stimuli responsive behaviours are contrasting. ABO shows stable mechanochromism but the protonation induced colour change is unstable. On the other hand, ABT shows stable acidochromism but luminescence changes induced by mechanical stress are reverted back quickly. A detailed study reveals that the variance in the heteroatoms in benzoxazole/benzothiazole moieties (oxygen and sulphur, respectively) significantly affects both the intra- and intermolecular electronic interactions of the molecules resulting in such observations. In the case of ABO, the benzoxazole moieties interact through weak edge-to-edge π-stacking, whereas in ABT, the ring overlap is more significant making the π-stacking a stronger face-to-face type, which helps in the restoration of the molecular ordering in ABT, which is energetically more viable. Regarding the acidochromic properties, the presence of more electronegative oxygen (compared to sulphur) in ABO draws electrons efficiently towards it making the nitrogen less basic and the complex formed between ABO and TFA less stable. On the other hand, electron density on the nitrogen in ABT might be higher compared to ABO due to the presence of less electronegative sulphur leading to the formation of a stable complex between ABT and TFA.

Photophysical and electroluminescence properties of bis(2′,6′-difluoro-2,3′-bipyridinato-N,C4′)iridium(picolinate) complexes: effect of electron-withdrawing and electron-donating group substituents at the 4′ position of the pyridyl moiety of the cyclometalated ligand

Herein, we have synthesized a series of 2′,6′-difluoro-2,3′-bipyridine cyclometalating ligands by substituting electron-withdrawing (–CHO, –CF3, and –CN) and electron-donating (–OMe and –NMe2) groups at the 4′ position of the pyridyl moiety and utilized them for the construction of five new iridium(III) complexes (Ir1–Ir5) in the presence of picolinate as an ancillary ligand. The photophysical properties of the developed iridium(III) compounds were investigated with a view to understand the substituent effects. The strong electron-withdrawing (–CN) group containing the iridium(III) compound (Ir3) exhibits highly efficient genuine green phosphorescence (λmax = 508 nm) at room temperature in solution and in thin film, with an excellent quantum efficiency (ΦPL) of 0.90 and 0.98, respectively. On the other hand, the –CF3 group substituted iridium(III) compound (Ir2) displays a sky-blue emission (λmax = 468 nm) with a promising quantum efficiency (ΦPL = 0.88 and 0.84 in solution and in thin film, respectively). The –CHO substituted iridium(III) complex (Ir1) showed greenish-yellow emission (λmax = 542 nm). Most importantly, the strong electron-donating –NMe2 substituted iridium(III) complex (Ir5) gives a structureless and a broad emission profile in the wavelength region 450 to 700 nm (λmax = 520 nm) with a poor quantum efficiency. An intense blue phosphorescence with impressive quantum efficiency, especially in thin-film noted in the case of the –OMe substituted iridium(III) complex (Ir4). Comprehensive density functional theory (DFT) and time-dependent DFT (TD-DFT) approaches have been performed on the ground and excited states of the synthesized iridium(III) complexes, in order to obtain information about the absorption and emission processes and to gain deeper insights into the photophysical properties. The combinations of a smaller ΔES1–T1 and higher contribution of 3MLCT in the emission process result in the higher quantum yields and lifetime values for complexes Ir1–Ir3. Multi-layered Phosphorescent Organic Light Emitting Diodes (PhOLEDs) were designed using the phosphorescent dopants Ir2, Ir3 and Ir4 and their elecroluminescence properties were evaluated. Compound Ir4 at a doping level of 5 wt% shows the best performance with an external quantum efficiency of 4.7%, in the nonoptimized device, and a power efficiency of 5.8 lm W−1, together with a true-blue chromacity CIEx,y = 0.15, 0.17 recorded at the maximum brightness of 33180 cd m−2.

N-heterocyclic carbene catalyzed annulation of enals to aurone analogs: synthesis of cyclopentene-fused spirobenzofuran-3-ones.

A nucleophilic heterocyclic carbene mediated homoenolate annulation of enals to aurone analogs leading to the efficient synthesis of cyclopentene-fused spirobenzofuran-3-ones is reported.

One-Pot MCR-Oxidation Approach toward Indole-Fused Heteroacenes

A straightforward synthetic route toward indole-fused heteroacenes was developed. The strategy is composed of a one-pot process starting with a multicomponent reaction of cyclohexanone, primary amine and N-tosyl-3-nitroindole followed by an oxidation step. The one-pot approach was found to be general, affording both symmetric and nonsymmetric indolo[3,2-b]indoles in good yields. The strategy was also utilized for accessing 5-ring fused benzo[g]indolo[3,2-b]indole. We could extend the methodology for the synthesis of benzothieno[3,2-b]indoles starting from 3-nitrobenzothiophene. The importance of the developed method was exemplified by performing the reaction sequence on gram scale and also by the synthetic transformations of indolo[3,2-b]indoles. In addition, the change in photophysical properties with extension of conjugation of the synthesized heteroacenes was studied.

Anticancer activity studies of cubebin isolated from Piper cubeba and its synthetic derivatives.

(-)-Cubebin, isolated from the seeds of Piper cubeba, and its five different types of derivatives (a total of 17), with varying functionalities, were tested for their in vitro anticancer activity against six human cancer cell lines (A549, K562, SiHa, KB, HCT116 and HT29) using MTT assay. Cubebin as well as its derivatives containing lactone and amide groups showed significant anticancer activity. In some of the tested cell lines, the amide derivatives showed higher activity. Morphological analysis indicated that these compounds act through apoptosis mediated pathway of cell death and we expect that these results will pave new paths in the development of novel anticancer agents by the derivatization of (-)-cubebin.

Antibacterial and antitubercular evaluation of dihydronaphthalenone-indole hybrid analogs

A new series of indole appended dihydronaphthalenone hybrid analogs (5a–t) have been synthesized through the Lewis acid catalyzed Michael addition of indoles to the arylidene/hetero arylidene ketones. All the synthesized derivatives are well characterized through the 1H‐NMR, 13C‐NMR, HRMS spectroscopic techniques, compound 5r was further confirmed through single crystal X‐ray analysis and screened for antibacterial and antitubercular activities. Among the synthesized compounds, the minimum inhibition concentration of 5l (against Escherichia coli) and 5o & 5p (against E. coli & Staphylococcus aureus) was found to be as low as 3.12 μg/ml as compared to the standard antibacterial drug ciprofloxacin 2.5 μg/ml. In antitubercular activity, compounds 5o and 5p with minimum inhibition concentration 6.25 μg/ml were found to be comparable with that of the drugs Pyrazinamide 5 μg/ml and Streptomycin 5 μg/ml. Compounds 5i, 5j, 5m, 5n, 5q, and 5r also showed promising activity against group of organisms tested.

NHC-Mediated Synthesis of Pyrrolo[2,1-a]isoquinolines and Their Photophysical Investigations

An NHC-mediated synthesis of pyrrolo[2,1-a]isoquinoline and indolizine derivatives with potential biological activity is reported (NHC=N-heterocyclic carbene). The preliminary photophysical studies of such compounds reveal that they have potential application in the sensing of volatile organic compounds (VOCs).

Expedient Synthesis of Indolo[2,3-b]quinolines, Chromeno[2,3-b]indoles, and 3-Alkenyl-oxindoles from 3,3′-Diindolylmethanes and Evaluation of Their Antibiotic Activity against Methicillin-Resistant Staphylococcus aureus

Easily accessible 3,3′-diindolylmethanes (DIMs) were utilized to generate a focused library of indolo[2,3-b]quinolines (2), chromeno[2,3-b]indoles (3), and 3-alkenyl-oxindoles (4) under 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-mediated oxidative conditions. DIMs with ortho-NHTosyl (NHTs) phenyl group afforded indolo[2,3-b]quinolines (2), whereas DIMs with ortho-hydroxy phenyl groups yielded chromeno[2,3-b]indoles (3) and 3-alkenyl-oxindoles (4). The mild conditions and excellent yields of the products make this method a good choice to access a diverse library of bioactive molecules from a common starting material. Two optimized compounds 2a and 2n displayed excellent activity against clinical isolates of methicillin-resistant Staphylococcus aureus (MRSA). Compound 2a showed the minimum inhibitory concentration values in the concentration between 1 and 4 μg/mL, whereas compound 2n revealed the values of 1–2 μg/mL. Furthermore, both the compounds were highly bactericidal and capable to kill the MRSA completely within 360 min. Collectively, the results suggested that both compounds 2a and 2n possess enormous potential to be developed as anti-MRSA agents.

Phytochemical investigation on Myristica fragrans stem bark

Abstract Myristica fragrans Houtt., the source of very important spice ‘nutmeg’ used world over is native to India, Indonesia, Sri Lanka, South Africa and Southeast Asia. Phytochemical investigation of M. fragrans stem bark led to the isolation of bis-aryl dimethyl tetrahydrofuran lignans, such as grandisin [(7S,8S,7′S,8′S)-3,3′,4,4′,5,5′-hexamethoxy-7,7′,8,8′-lignan] and (7S,8S,7′R,8′R)-3,3′,4,4′,5,5′-hexamethoxy-7,7′,8,8′-lignan along with important lignans and neolignans, licarinA, licarin B, odoratisol A, (2S, 3R)-7-methoxy-3-methyl-5-((E)-prop-1-enyl)-2-(5-methoxy,3,4-methylenedioxyphenyl)-2,3-dihydrobenzofuran, elemicin, fragransin B1, raphidecursinol B, erythro-(7S,8R)-Δ8′-4,7-dihydroxy-3,5,3′-trimethoxy-8-O-4′-neolignan, erythro-(7S,8R)-Δ8′-7-hydroxy-3,4,3′,5′-tetramethoxy-8-O-4′-neolignan, surinamensin.and β-sitosterol. Structures of the 12 compounds isolated were unambiguously identified by various spectroscopic methods. The former two compounds were isolated from M. fragrans for the first time. Furthermore, the X-ray crystal structure of odoratisol A is reported in this paper for the first time.