Polymorphism Dependent Cytotoxicity, Cellular Uptake, and Live Cell Imaging Studies on Napthalimide-Vinyl-Phenothiazine Conjugate.

Polymorphism-dependent cytotoxicity and cellular uptake of drug molecules have been studied for the past two decades. However, the visualization of polymorph-dependent cellular uptake and cytotoxicity using microscopy imaging techniques has not yet been reported. The luminescent polymorph is an ideal candidate to validate the above hypothesis. Herein, we report the polymorph-dependent cellular uptake, cytotoxicity, and bio-imaging functions of polymorphs 1Y and 1R of a naphthalimide-phenothiazine dyad. These polymorphs show different luminescence colors in the solid state and exhibit aggregation-induced enhanced emission (AIEE) in the DMSO-Water mixture. Bioimaging, cytotoxicity assay, and fluorescence-activated cell sorting (FACS) studies revealed that these polymorphs show different levels of cytotoxicity, cellular uptake, localization, and imaging potential. Detailed photophysical, morphological, and biological studies revealed that the difference in molecular conformation in these polymorphs enables them to form aggregates of different sizes and morphology, which leads to the differential uptake of these into the cells and consequently shows different cytotoxicity and imaging potentials.

Heteroatom-Promoted Polyhexagonal Saddle-Shaped Molecular Structures and their Supramolecular Coassembly with C60.

Molecules with curved architecture can exhibit unique optoelectronic properties due to the concave-convex π-surface. However, synthesizing negatively curved saddle-shaped aromatic systems has been challenging due to the internal structural strain. Herein, we report the facile synthesis of two polyhexagonal molecular systems, 1 and 2, with saddle shape geometry by judiciously varying the aromatic moiety, avoiding the harsh synthetic methods as that of heptagonal aromatic saddle systems. The unique geometry preferences of B, N, and S furnish suitable curvature to the molecules, featuring saddle shape. The saddle geometry also enables them to interact with fullerene C60 , and the supramolecular interactions of fullerene C60 with 1 and 2 modify their optoelectronic properties. Crystal structure analysis reveals that 1, with a small π-surface, forms a double columnar array of fullerenes in the solid state. In contrast, 2 with a large π-surface produces a supramolecular capsule entrapping two discrete fullerenes. The intermolecular interactions between B, N, S, and the aryl-π surface of the host and C60 guest are the stabilizing factors for creating these supramolecular structures. Comprehensive computational, optical, and Raman spectroscopic studies establish the charge transfer interactions between B-N doped heterocycle host and fullerene C60 guest.

Shape and Phase-Controlled One-Pot Synthesis of Air Stable Cationic AgCdS Nanocrystals, Optoelectronic and Electrochemical Hydrogen Evolution Studies.

CdS-based materials are extensively studied for photocatalytic water splitting. By incorporating Ag+ into CdS nanomaterials, the catalyst's charge carrier dynamic can be tuned for photo-electrochemical devices. However, photo-corrosion and air-stability of the heterostructures limit the photocatalytic device's performance. Here, a one-pot, single molecular source synthesis of the air-stable AgCdS ternary semiconductor alloy nanostructures by heat-up method is reported. Monoclinic and hexagonal phases of the alloy are tuned by judicious choice of dodecane thiol (DDT), octadecyl amine (ODA), and oleyl amine (OLA) as capping agents. Transmission electron microscope (TEM) and powder X-ray diffraction characterization of the AgCdS alloy confirm the monoclinic and hexagonal phase (wurtzite) formation. The high-resolution TEM studies confirm the formation of AgCdS@DDT alloy nanorods and their shape transformation into nano-triangles. The nanoparticle coalescence is observed for ODA-capped alloys in the wurtzite phase. Moreover, OLA directs mixed crystal phases and anisotropic growth of alloy. Optical processes in AgCdS@DDT nano-triangles show mono-exponential decay (3.97 ± 0.01 ns). The monoclinic phase of the AgCdS@DDT nanorods exhibits higher electrochemical hydrogen evolution activity in neutral media as compared to the AgCdS@ODA/OLA alloy nanocrystals. DDT and OLA-capped alloys display current densities of 14.1 and 14.7 mA cm-2 , respectively, at 0.8 V (vs RHE).

Pyrrole ßC-B-N Fused Porphyrins: Molecular Structures and Opto-Electrochemical Studies.

Herein, we report the design, synthesis, structure, and electrochemical study of doubly ßC-B-N fused Ni(II) porphyrins (1-trans, 1-cis, 2-trans, and 2-cis). These compounds have been synthesized from A2B2 type dipyridyl Ni(II) porphyrins (Ar=Ph for 1 a; Ar=C6F5 for 2 a) via Lewis base-directed electrophilic aromatic borylation reactions. The solution state structures of these compounds have been established using 1H NMR, 11B NMR, 1H-1H COSY, 1H-13C HSQC, and 19F-13C HSQC NMR techniques. Single crystal X-ray analysis have revealed that 1-trans, 1-cis, and 2-trans adopt ruffled conformations, with alternate meso-carbons on the opposite sides of the mean porphyrin plane. The Soret bands in the absorption spectra of the B-N fused molecules are ~40 nm redshifted compared to unfused Ni(II) porphyrin precursors. The B-N fusion have diminished the redox potential of fused porphyrins. Although 1-trans and 1-cis, show four oxidation processes, 2-trans and 2-cis show only three oxidation processes. DFT studies have revealed that the tetrahedral geometry of the boron has induced a twist in the π-conjugation, which destabilizes the HOMO and stabilizes the LUMO in 1-trans, 1-cis, 2-trans, and 2-cis.

Chiral B-N AIEgens: Intense Blue Circularly Polarized Luminescence and Piezochromism.

We present a new class of blue circularly polarized luminescent emitters based on tetraarylaminoborane (TAAB) with considerable dissymmetry factor in the solid state. The chiral pendant 1-phenylethylamine in BN-RR and BN-SS imparts chirality to the core chromophore, resulting in circularly polarized luminescence signals (glum = 0.8 × 10-3) with a quantum yield of 33% in the crystalline state. This novel set of compounds also showcases intriguing thermally reversible piezochromism.

Single Molecular Persistent Room-Temperature Phosphorescence and Circularly Polarized Luminescence from Binaphthol-Decorated Optically Innocent Cyclotriphosphazenes.

Circularly polarized luminescence (CPL) features of BINOL-decorated cyclotriphosphazenes (CPs) are reported for the first time. The luminescence dissymmetry factor (glum ) of these compounds in chloroform solutions and polymethyl methacrylate (PMMA) thin films with wt 1 % doping concentrations are found to be 1.0×10-3 , and 2.9×10-3 , respectively. However, no CPL signal is observed for the pristine solids. The enantiomers (CP-(R)/CP-(S)) show ultraviolet photoluminescence (~350-360 nm) in solution and the solid state. These compounds show ~10 times larger absolute photoluminescence quantum yield (PLQY) than the simple BINOLs in the solutions state. In the solid state, CP-(R) shows larger PLQY than binaphthol-(R); in contrast, the S enantiomer shows lower PLQY than binaphthol-(S); this indicates that the isomer-dependent solid-state packing of these compounds plays a crucial role in controlling the PL. Thin films with more than 1 % doping concentration and pristine solids of these compounds do not show persistent room-temperature phosphorescence (pRTP) due to concentration-caused quenching. However, thin films with wt 1 % of these chiral emitters exhibit pRTP characteristics with a ~159-343 ms lifetime under vacuum. Theoretical calculations reveal that the cyclophosphazene acts as an optically innocent dendritic core, and the optical features of these compounds are dictated by the pendent BINOL chromophore.

Molecular Persistent Room-Temperature Phosphorescence from Tetraarylaminoboranes.

Herein, we report the synthesis, molecular structure, and optical features of tetrarylaminoboranes 1 (Mes2B-N(Ph)(C10H7)) and 2 (Mes2B-N(Ph)(C14H9)). In the solution state, 1 shows aggregation-induced emission enhancement and color switching, while 2 displays emission color switching and aggregation-caused quenching. At 77 K, frozen solutions of 1 show delayed fluorescence (DF) and phosphorescence, whereas 2 display only DF. Pristine solids of 1 and 2 showed delayed fluorescence under ambient conditions; however, crystals of both compounds show no phosphorescence under similar conditions. Polymethyl methacrylate thin films of 1 (1 wt % doping concentration) exhibit persistent room-temperature phosphorescence (pRTP) lasting for ∼0.5 s. In contrast, 2 does not show phosphorescence under similar conditions. Systematic photophysical studies and theoretical (DFT and TD-DFT) calculations are performed on these molecules to rationalize their intriguing optical characteristics.

Crystallization induced room-temperature phosphorescence and chiral photoluminescence properties of phosphoramides.

We report the design and synthesis of a series of room temperature phosphorescent phosphoramides TPTZPO, TPTZPS, and TPTZPSe with a donor (phenothiazine)-acceptor (P = X, X = O, S, and Se) architecture. All the compounds show structureless fluorescence with a nanosecond lifetime in dilute solutions. However, these compounds show dual fluorescence and room temperature phosphorescence (RTP) in the solid state. Both the intensity and energy of luminescence depend on the heteroatom attached to the phosphorus center. For example, compound TPTZPO with the P[double bond, length as m-dash]O unit exhibits fluorescence at a higher energy region than TPTZPS and TPTZPSe with the P[double bond, length as m-dash]S and P[double bond, length as m-dash]Se groups, respectively. Crystalline samples of TPTZPO, TPTZPS, and TPTZPSe show stronger RTP than the amorphous powder of respective compounds. Detailed steady-state, time-resolved photoluminescence and computational studies established that the 3n-π* state dominated by the phenothiazine moiety is the emissive state of these compounds. Although TPTZPS and TPTZPSe crystallized in the chiral space group, only TPTZPSe showed chiroptical properties in the solid state. The luminescence dissymmetry factor (g lum) value of TPTZPS is small and below the detection limit, and a CPL spectrum could not be observed for this compound.

Synthesis and Characterization of Far-Red Emissive Boron-Based Triads Showing Large Stokes Shifts: Optical, TRANES, and Electrochemical Studies.

Herein, we report the design and synthesis of far-red emissive boryl-thiophene-BODIPY triads 1-3. The π-conjugation length and electronic communication between borane and BODIPY moieties are tuned by judiciously varying the size of the oligothiophene spacer in these triads (1, terthiophene; 2, quarterthiophene; and 3, pentathiophene). Conjugates 1-3 showed intriguing triple emissions in the blue to far-red regions. Detailed optical, time-resolved decay kinetics, time-resolved area-normalized emission spectra (TRANES), fluoride binding, and computational studies suggest that the multiple emissions in these triads are due to an inefficient transfer of energy from the boryl-oligothiophene to the BODIPY unit. In addition, all of the conjugates showed a ratiometric fluorescence response to fluoride ions.

Effect of the Molecular Conformation on Excitation Energy Transfer in Conformationally Constrained Boryl-BODIPY Dyads.

We studied the dual emission characteristics of a series of boryl-BODIPYs (1-6) comprised of triarylborane (TAB) as an energy donor and BODIPY as an energy acceptor. The molecular conformations of dyads 1-6 were systematically tuned by judiciously changing the spacer that bridged the boryl and BODIPY moieties. Frontier molecular orbitals (FMOs) are localized in 3, 4, and 6 with a twisted molecular conformation. In contrast, FMOs are significantly delocalized in 1, 2, and 5 with the least-twisted molecular conformation. Dyads 1-6 showed dual emission features when they were excited at the TAB-dominated absorption band. However, the ratio between the two emission bands in 1-6 significantly varied depending on the molecular conformations. Systematic photoluminescence (PL) studies (both steady-state and time-resolved PL) together with computational, crystal structure, and anion binding studies established that the frustrated excited-state energy transfer from borane to BODIPY is the cause of the dual emission features in these molecular dyads. These studies also revealed that the energy transfer from borane to BODIPY can be elegantly tuned by modulating the dihedral angle between these two moieties.

Design, Synthesis, and Temperature-Driven Molecular Conformation-Dependent Delayed Fluorescence Characteristics of Dianthrylboron-Based Donor-Acceptor Systems.

We report a simple and novel molecular design strategy to enhance rISC in boron-based donor-acceptor systems to achieve improved delayed fluorescence characteristics. Dianthrylboryl ((An)2B)-based aryl aminoboranes 1 (donor: phenothiazine) and 2 (donor: N,N-diphenylamine) were synthesized by a simple one-pot procedure. The energy of the electronic excited states in 1 and 2 were modulated by varying the arylamine donor strength and electronic coupling between D and A moieties. The presence of a large π-system (anthryl moiety) on boron enhances the electronic communication between donor arylamine and acceptor boryl moieties, and hence, both 1 and 2 exhibit delayed fluorescence characteristics in a broad range of temperatures (80-300 K). Single crystal X-ray analysis and temperature-dependent photophysical studies together with theoretical studies were carried out to rationalize the observed intriguing optical signatures of 1 and 2.

Molecular Conformational Effect on Optical Properties and Fluoride Induced Color Changes in Triarylborane-Vinylbithiophene-BODIPY Conjugates.

Three new triads [bis(mesityl)boryl (Mes2B)-vinylbithiophene-BODIPY] bearing zero (1), two (2), and four (3) methyl groups on the BODIPY core are synthesized, and their optical properties are reported. The vinyl linker between the thiophene rings in the spacer moiety improved the electronic communication between the boryl and BODIPY units. It displayed a bathochromic shift in the absorption and emission spectra compared to the Mes2B-bithiophene-BODIPY triad reported elsewhere. These compounds exhibit intriguing multiple-emission features due to an incomplete energy transfer from donor borane to the acceptor BODIPY unit. These compounds' photoluminescence color can be conveniently fine-tuned by fluoride binding at the coordinatively unsaturated tricoordinate boron center. Triad 3, with a rigid molecular structure, showed a sharp emission band, whereas triads 1 and 2, with flexible molecular structures, displayed broad emission bands with a robust bathochromic shift, ascribed to their excited state structural reorganizations. These triads selectively bind fluoride ions and show colorimetric responses, which can be seen with an unaided eye. DFT computational studies were performed to rationalize the optical signatures of these compounds.

Delayed Fluorescence, Room Temperature Phosphorescence, and Mechanofluorochromic Naphthalimides: Differential Imaging of Normoxia and Hypoxia Live Cancer Cells.

We study the effect of molecular conformation on the electronic coupling between the donor amines and acceptor 1,8-naphthalimide (NPI) in a series of D-A systems 1-4 (A = NPI; D = phenothiazine, phenoxazine, carbazole, diphenylamine, respectively, for 1, 2, 3, and 4). Weakly coupled systems show dual emission in the solution state, while strongly coupled systems show single emission bands. The energy of transitions and photoluminescence (PL) quantum yield are sensitive to the molecular conformation and donor strength. These compounds show delayed emission in the solutions and aggregated state and phosphorescence in the solid state. Compounds 3 and 4 with weak donors exhibit intermolecular slipped π···π interactions in the solid state and consequently exhibit dual (intra- and inter-) phosphorescence at low temperature. Steady state and time-resolved PL studies at variable temperature together with computational and crystal structure analysis were used to rationalize the optical properties of these compounds. The delayed emission of these compounds is sensitive to molecular oxygen; accordingly, these molecules are utilized for differential imaging of normoxia and hypoxia cancer cells.

Triarylborane-Appended Anils and Boranils: Solid-State Emission, Mechanofluorochromism, and Phosphorescence.

Herein, the design, synthesis, optical properties, and mechanofluorochromism characteristics of a series of conjugates having covalently linked triarylborane (TAB) and anil/boranil units (TAB-anil: 1 a-3 a and TAB-boranil: 1-3) are reported. The electronic interactions between TAB and anil/boranil in 1 a-3 a and 1-3 were fine-tuned by changing the boryl moiety's position on the phenyl spacer connecting the BMes2 (Mes=mesityl) and anil/boranil units. A boryl moiety at the meta position (1 a) of the phenyl spacer stabilizes the enolic form (E-OH), whereas a boryl moiety at the para position (2 a and 3 a) stabilizes the keto form (Z-NH) in the solid state. However, in solution 1 a, 2 a, and 3 a exhibit keto-enol tautomerism in both ground and excited states. Compounds 1 a-3 a and 1-3 show red-shifted absorption compared with 4 a and 4, which are devoid of TAB moieties, which indicate effective participation of an empty p orbital on the boron center in 1 a-3 a and 1-3. Compounds 1 and 2 showed fluorescence variations in response to external stimuli such as mechanical grinding. Long phosphorescence lifetimes of 18-46 ms were observed for compounds 1-3. The observed optical properties of 1 a-3 a and 1-3 are rationalized in the context of quantum mechanical calculations.

Effect of Branching on the Delayed Fluorescence and Phosphorescence of Simple Borylated Arylamines.

A donor-π-acceptor strategy is being well exploited in several fields in view of their robust optical properties. However, the impact of branching in quadrupolar [A-(π-D)2] and octupolar [A-(π-D)3] molecules in comparison to parent dipolar (A-π-D) molecules on the delayed fluorescence and phosphorescence properties is seldom explored. We have presented herein the distinct and contrasting optical properties of a tridurylborane core bearing -NH2 (1-3) and -NMe2 (4-6) donor moieties, wherein the number of donors is increased systematically. Because of propeller molecular architecture, the donor and acceptor are weakly coupled, and the frontier molecular orbitals are spatially localized. All of the compounds show delayed fluorescence under ambient conditions and persistent phosphorescence at low temperature. Solvent-dependent studies and temperature-dependent luminescence measurements established that quadrupolar (2 and 5) and octupolar (3 and 6) compounds underwent symmetry breaking in the excited state. Curiously, delayed fluorescence and phosphorescence spectra are found to be blue-shifted and follow the same trend as the fluorescence upon an increase in the branches. The highest quantum yield was observed for dipolar compounds. Besides, the phosphorescence lifetime decreases with an increase in the number of branches. These interesting experimental observations are further supported by quantum-mechanical calculations.

Aggregation-Induced and Polymorphism-Dependent Thermally Activated Delayed Fluorescence (TADF) Characteristics of an Oligothiophene: Applications in Time-Dependent Live Cell Multicolour Imaging.

Typically, molecules with a twisted donor-acceptor (D-A) architecture have been exploited for constructing thermally activated delayed fluorescence (TADF) materials. Herein, we report the first example of a thiophene-based thermally activated delayed fluorescent molecule without a D-A architecture. Compound 1 (2,5-bis(2,2-di(thiophen-2-yl)vinyl)thiophene) is conformationally flexible and shows weak fluorescence in the solution state but displays bright TADFin both condensed and solid states. Compound 1 crystallized in two different polymorphs (1 a and 1 b). Interestingly, both polymorphs show distinctly different TADF features. The broad spectral features and the TADF characteristics of 1 have been explored for the time-dependent multicolor (green, yellow and red) imaging of living cells.

Room temperature phosphorescent triarylborane functionalized iridium complexes.

We report a series of room temperature phosphorescent compounds 1-6 composed of triarylborane (TAB) and cyclometallated iridium complexes. The optical characteristics such as energy of transition and luminescence quantum yield of these compounds can be conveniently fine-tuned by judiciously varying the cyclometallating ligand and the spacer between boron and iridium centers. Compounds 1-6 exhibit bright phosphorescence with the emission color ranging from green to red under a N2 atmosphere. A maximum quantum yield of 0.95 was observed for complex 2. Complexes 1-6 exhibit a rare type of dual emission from singlet and triplet excited states under ambient conditions. The experimental observations are well supported by the theoretical calculations.

Borylated perylenediimide: self-assembly, photophysics and sensing application.

Triarylboryl appended perylenediimide (PDI-TAB) is designed and synthesized. The incorporation of triarylboranes (TABs) decreases self-aggregation and increases the solubility of PDI-TAB in common organic solvents. Fluorescence emission colors ranging from red, yellow and green are realized by judiciously modulating the concentration of PDI-TAB in solution. The morphology and dimensions of the self-assemblies formed by PDI-TAB can be controlled by changing the experimental conditions. For example, PDI-TAB forms fibers of finite length when bulk powder is dispersed in methanol; it shows flexible lengthy 1D fibers when dichloromethane solution of PDI-TAB is injected into methanol solvent. PXRD analysis indicates that the molecular organization remains the same in both cases. PDI-TAB functions as a selective fluorogenic sensor for toxic fluoride anions; the sensing mechanism is explained by using theoretical calculations.

Renaissance of Organic Triboluminescent Materials.

Solid-state luminescence of organic dyes is an elusive frontier, and understanding and designing solid-state stimuli-responsive materials is not trivial. "Mechanoluminescence" (ML) or "triboluminescence" (TL), which is associated with fracture or force-initiated luminescence from a material, is currently attracting new interest. Fracturing the surfaces of organic crystals ordered in noncentrosymmetric space groups can electronically excite the surface and neighboring molecules through piezo- or pyroelectric effects, and this can result in luminescence when the molecules relax back to their ground states. The combined duration of these two consecutive phenomena leads to force-generated luminescence or TL. Although TL has been known for a very long time, examples of TL-active materials are scarce, but are increasing as synthetic and characterization procedures develop. The question is now whether the relatively rare phenomenon of TL needs to be reevaluated to obtain a broader understanding of the subject.

Catalyst- and Template-Free Ultrafast Visible-Light-Triggered Dimerization of Vinylpyridine-Functionalized Tetraarylaminoborane: Intriguing Deep-Blue Delayed Fluorescence.

A photoredox-catalyst- and template-free sunlight-induced molecular dimerization of a vinylpyridine-functionalized tetraarylaminoborane (TAAB) has been accomplished for the first time. The reaction is quantitative, highly regioselective, and thermally irreversible. The presence of the propeller-shaped TAAB framework allows selective photodimerization of one of the two vinyl pyridine units. Monomer 1 and photodimer 2 exhibit distinct photophysical properties with delayed fluorescence (DF) both in solution and the solid state, which was confirmed by steady-state and time-resolved luminescence studies. Quantum mechanical calculations were performed to support the experimental observations. Our new approach using [2+2] cycloaddition chemistry paves the way for the development of highly sought-after deep-blue DF materials.