Self-assembled organic and hybrid materials derived from oligo-(p-phenyleneethynylenes).

Oligo-(p-Phenyleneethynylenes) (OPEs) have garnered widespread interest over the past three decades due to their excellent opto-electronic properties. However, the chief focus has been on the use of mainly small molecules or polymeric systems for the study of their structural diversity in opto-electronic applications. Recently, researchers have started delving deeper into their utility in material applications. Purely organic materials such as supramolecular polymers, self-assembled nanostructures, nanostructured organogels and single-crystalline materials derived from OPEs have already been developed and researched. Chirality has also been introduced into these systems. Additionally, these have shown physical properties such as polymorphism, liquid crystallinity, melt formation, mechanochromism, etc. All these materials have also shown excellent luminescence properties with high quantum yield and some have even shown energy harvesting properties. There have also been sporadic reports on OPE linker based hybrid systems such as metallogels and metal-organic framework (MOF) structures where structural analysis reveals the origin of tunable emission in these materials. Furthermore, by innovative structural design, unexplored properties of OPEs such as water repellency, bioimaging, drug delivery, photocatalysis, energy transfer, nanomorphology control, photoconductivity, and colour tunability could be achieved. This feature article will, therefore, encompass a detailed discussion on the development of this field as well as the analysis of the properties realized in OPE derived self-assembled supramolecular materials. The main focus will be on the following classes of materials: soft supramolecular materials, crystalline supramolecular π-systems, nanoscale metal-organic frameworks (NMOFs) and bulk metal-organic frameworks (MOFs) and how their application horizon has been expanded by integrating OPEs into their structures.

Photochromic Conjugated Microporous Polymer Manifesting Bio-Inspired pcFRET and Logic Gate Functioning.

Design and synthesis of solid-state photochromic materials remain a challenge because of high structural constrain. However, this can be mitigated in attaining structural flexibility by introducing permanent porosity into the system. Here, we report for the first time the design and synthesis of a photochromic conjugated microporous polymer (pcCMP) by assembling photochromic dithienylethene aldehyde and benzene-1,3,5-tricarbohydrazide. The yellow photo-isomer pcCMP-O gets converted to a deep-green photo-isomer pcCMP-C by UV-light irradiation, which can be reverted to pcCMP-O by visible light or thermal treatment. Owing to the thermo-irreversible nature, the pcCMP is found to be suitable for designing an INH functioning logic gate. pcCMP-C shows highly enhanced conductivity (92 times) because of enhanced conjugation compared to pcCMP-O. Furthermore, we demonstrate the bio-inspired photo-switchable pcFRET process by encapsulation of a red-emissive green fluorescent protein (gfp) chromophore analogue into the pcCMP. This material shows high processibility and has been exploited further for secret writing.

Photoswitchable J-Aggregated Processable Organogel by Integrating a Photochromic Acceptor.

A novel π-chromophoric 1,4-bis(anthracenylethynyl)benzene (BAB)-based highly emissive J-aggregated organogel has been synthesized and characterized. Single-crystal structure determination of asymmetric π-chromophoric bola-amphiphilic BAB1 (dodecyl and triethyleneglycolmonomethylether containing side chains of bis(anthracenylethynyl)benzene) supports J-aggregation. Further, a photochromic acceptor chromophore, 4,4'-(perfluorocyclopent-1-ene-1,2-diyl)bis(5-methylthiophene-2-carbaldehyde), is noncovalently encapsulated in the gel and photoswitching studies have been performed based on photochromic Förster resonance energy transfer. The modulated emission of the processable soft material is further exploited for rewritable display. However, BAB2 (dodecyl side chain on both sides) does not show gelation property due to its low solubility.

Dynamic Resolution of Piezosensitivity in Single Crystals of π-Conjugated Molecules.

Targeted synthesis of piezoresponsive small molecules and in-depth understanding of their mechanism is of utmost importance for the development of smart devices. This work reports the synthesis, structure and piezosensitivity of a bola-amphiphile 1,4-bis(pentyloxy)-2,5-bis(2-pyridineethynyl)-benzene (C5-PPB). Depending on the rate of compression, two different phases in C5-PPB can be generated. The ambient-pressure α-phase is stable up to 0.8 GPa, beyond which it undergoes an isostructural transformation to ß-phase, accompanied by a clearly visible elongation of the crystal. This α-to-ß phase transition requires the sample to be compressed slowly. When quickly compressed, phase α persists to about 1.5 GPa, beyond which its amorphization starts, accompanied by the appearance of irregular grooves on the largest faces. Mechanical pressure also affects the optical property of C5-PPB, which shows reversible mechanochromism with a green to cyan transformation in the emission, associated with a 15 nm shift in the maxima. The conductivity of C5-PPB as a direct outcome of its crystal packing has also been studied.

Solvent Adaptive Dynamic Metal-Organic Soft Hybrid for Imaging and Biological Delivery.

A solvent responsive dynamic nanoscale metal-organic framework (NMOF) [Zn(1 a)(H2 O)2 ] has been devised based on the self-assembly of ZnII and asymmetric bola-amphiphilic oligo-(p-phenyleneethynylene) (OPE) dicarboxylate linker 1 a having dodecyl and triethyleneglycolmonomethylether (TEG, polar) side chains. In THF solvent, NMOF showed nanovesicular morphology (NMOF-1) with surface decorated dodecyl chains. In water and methanol, NMOF exhibited inverse-nanovesicle (NMOF-2) and nanoscroll (NMOF-3) morphology, respectively, with surface projected TEG chains. The pre-formed NMOFs also unveiled reversible solvent responsive transformation of different morphologies. The flexible NMOF showed cyan emission and no cytotoxicity, allowing live cell imaging. Cisplatin (14.4 wt %) and doxorubicin (4.1 wt %) were encapsulated in NMOF-1 by non-covalent interactions and, in vitro and in vivo drug release was studied. The drug loaded NMOFs exhibited micromolar cytotoxicity.

In situ Stabilization of Au and Co Nanoparticles in a Redox-Active Conjugated Microporous Polymer Matrix: Facile Heterogeneous Catalysis and Electrocatalytic Oxygen Reduction Reaction Activity.

We report a novel in situ method for synthesis of metal nanoparticles (NPs)-CMP (conjugated microporous polymer) composites based on a redox-active, donor-acceptor CMP, tris-(4-aminophenyl)amine (TPA)-perylenediimide (PDI). The TPA-PDI CMP, comprising triphenylamine as an electron donor and PDI as an acceptor, showed stable charge-separated state and semiconducting behavior. Further, TPA-PDI CMP has been exploited for in situ stabilization of metal (Au and Co) NPs, and two novel nanocomposites (Au@TPA-PDI and Co@TPA-PDI) were prepared. The catalytic reduction of nitro aryls to amino aryls was studied using Au@TPA-PDI, which showed excellent yields and fast kinetics. The CMP itself was found to show good activity as a metal-free oxygen reduction reaction (ORR) electrocatalyst with an onset potential of 0.82 V. Stabilizing merely 2.56 wt % Co nanoparticles in the CMP matrix improved the electrochemical ORR activity of as-synthesized TPA-PDI immensely and showed an onset potential of 0.91 V, which has also been supported by density functional theory (DFT) calculations.

Solvent-Modulated Emission Properties in a Superhydrophobic Oligo( p-phenyleneethynylene)-Based 3D Porous Supramolecular Framework.

A chromophoric oligo( p-phenyleneethynylene) (OPE) bola-amphiphile with dioxyoctyl side chains (H2OPE-C8) has been self-assembled with CdII to form a 1D coordination polymer, {Cd(OPE-C8)(DMF)2(H2O)} (1), which is further interdigitated to form a 2D network. Such 2D networks are further interwoven to form a 3D supramolecular framework with surface-projected alkyl chains. The desolvated framework showed permanent porosity, as realized from the CO2 adsorption profile. 1 showed high water contact angles, portraying its superhydrophobic nature. 1 also showed a linker-based cyan luminescence. Solvent removal led to a bathochromic shift in emission into the green region. Resolvation with N, N-dimethylformamide brought back the original cyan emission, whereas for tetrahydrofuran, ethanol, and methanol, it persisted at an intermediate state. Density functional theory calculations unraveled that, twisting of the OPE phenyl rings generated the red shift in emission.

Nanovesicular MOF with Omniphilic Porosity: Bimodal Functionality for White-Light Emission and Photocatalysis by Dye Encapsulation.

A new π-chromophoric and asymmetric bola-amphiphilic oligo-( p-phenylene ethynylene)-based tetracarboxylate (OPE-TC1) linker was designed, synthesized, and self-assembled with Zn(OAc)2. The resulting nanoscale metal-organic framework (MOF) {Zn2(OPE-TC1)} n (NMOF-1) showed a vesicular morphology and permanent porosity with omniphilic pore surface. NMOF-1 showed cyan emission with high quantum efficiency (49%). The omniphilicity of the pore was utilized to incorporate ambipolar dye sulforhodamine G (SRG) to tune the band gap as well as to get pure white-light emission. Furthermore, the polar pore surface of NMOF-1 allowed facile diffusion of the substrate for efficient photocatalytic activity. The dye-encapsulated framework further showed enhanced dihydrogen production by 1.75-fold compared to that from the as-synthesized NMOF-1 because of the modulated band gap and high excited state lifetime. As a control experiment, we have synthesized a MOF (MOF-OMe) with an OPE-TC2 linker having -OMe functional groups that did not show nanoscale architecture. This suggested the important role of unsymmetrical bola-amphiphilicity in nanostructuring. This rational design of a chromophoric linker resulted in a nanoscale MOF with omniphilic porosity to achieve bimodal functionality in clean energy applications.

Metallophthalocyanine-based redox active metal-organic conjugated microporous polymers for OER catalysis.

We report the design and synthesis of two Co2+ and Zn2+ phthalocyanine (PC)-based redox active metal-organic conjugated microporous polymers (MO-CMP), CoCMP and ZnCMP, respectively, obtained by a Schiff base condensation reaction. CoCMP, where Co2+ is stabilized by N4-coordination of PC, has shown stable and efficient electrocatalytic activity towards the OER with a low overpotential of 340 mV.

Pure white light emission and charge transfer in organogels of symmetrical and unsymmetrical π-chromophoric oligo-p-(phenyleneethynylene) bola-amphiphiles.

Two novel bola-amphiphilic oligo-p-(phenyleneethynylene) (OPE) dicarboxylates have been synthesized having non-polar and mixed-polar side chains. This led to gelation in both with vesicular morphology. Upon in situ loading of a suitable dye and redox-active molecule, pure white light emitting and charge transfer (CT)-gels, respectively, were realized.

Reversible Polymorphism, Liquid Crystallinity, and Stimuli-Responsive Luminescence in a Bola-amphiphilic π-System: Structure-Property Correlations Through Nanoindentation and DFT Calculations.

We report the design, synthesis, detailed characterization, and analysis of a new multifunctional π-conjugated bola-amphiphilic chromophore: oligo-(p-phenyleneethynylene)dicarboxylic acid with dialkoxyoctadecyl side chains (OPE-C18-1). OPE-C18-1 shows two polymorphs at 123 K (OPE-C18-1') and 373 K (OPE-C18-1″), whose crystal structures were characterized via single crystal X-ray diffraction. OPE-C18-1 also exhibits thermotropic liquid crystalline property revealing a columnar phase. The inherent π-conjugation of OPE-C18-1 imparts luminescence to the system. Photoluminescence measurements on the mesophase also reveal similar luminescence as in the crystalline state. Additionally, OPE-C18-1 shows mechano-hypsochromic luminescence behavior. Density functional theory (DFT)-based calculations unravel the origins behind the simultaneous existence of all these properties. Nanoindentation experiments on the single crystal reveal its mechanical strength and accurately correlate the molecular arrangement with the liquid crystalline and mechanochromic luminescence behavior.

Self-cleaning MOF: realization of extreme water repellence in coordination driven self-assembled nanostructures.

Bio-inspired self-cleaning surfaces have found industrial applications in oil-water separation, stain resistant textiles, anti-biofouling paints in ships etc. Interestingly, self-cleaning metal-organic framework (MOF) materials having high water contact angles and corrosion resistance have not been realized so far. To address this issue, we have used the fundamentals of self-assembly to expose hydrophobic alkyl chains on a MOF surface. This decreases the surface free energy and hence increases hydrophobicity. Coordination directed self-assembly of dialkoxyoctadecyl-oligo-(p-phenyleneethynylene)dicarboxylate (OPE-C18 ) with ZnII in a DMF/H2O mixture leads to a three dimensional supramolecular porous framework {Zn(OPE-C18)·2H2O} (NMOF-1) with nanobelt morphology. Inherently superhydrophobic and self-cleaning NMOF-1 has high thermal and chemical stability. The periodic arrangement of 1D Zn-OPE-C18 chains with octadecyl alkyl chains projecting outward reduces the surface free energy leading to superhydrophobicity in NMOF-1 (contact angle: 160-162°). The hierarchical surface structure thus generated, enables NMOF-1 to mimic the lotus leaf in its self-cleaning property with an unprecedented tilt angle of 2°. Additionally, superhydrophobicity remains intact over a wide pH range (1-9) and under high ionic concentrations. We believe that such a development in this field will herald a new class of materials capable of water repellent applications.

Highly Luminescent Microporous Organic Polymer with Lewis Acidic Boron Sites on the Pore Surface: Ratiometric Sensing and Capture of F(-) Ions.

Reversible and selective capture/detection of F(-) ions in water is of the utmost importance, as excess intake leads to adverse effects on human health. Highly robust Lewis acidic luminescent porous organic materials have potential for efficient sequestration and detection of F(-) ions. Herein, the rational design and synthesis of a boron-based, Lewis acidic microporous organic polymer (BMOP) derived from tris(4-bromo-2,3,5,6-tetramethylphenyl)boron nodes and diethynylbiphenyl linkers with a pore size of 1.08 nm for selective turn-on sensing and capture of F(-) ion are reported. The presence of a vacant pπ orbital on the boron center of BMOP results in intramolecular charge transfer (ICT) from the linker to boron. BMOP shows selective turn-on blue emission for F(-) ions in aqueous mixtures with a detection limit of 2.6 µM. Strong B-F interactions facilitate rapid sequestration of F(-) by BMOP. The ICT emission of BMOP can be reversibly regenerated by addition of an excess of water, and the polymer can be reused several times.

Series of dicyanamide-interlaced assembly of zinc-Schiff-base complexes: crystal structure and photophysical and thermal studies.

Four new dicyanamide (dca) bridged multinuclear Zn(II)-Schiff-base complexes, {[Zn2L(1)(µ1,5-dca)dca]·CH3OH}2 (1), [Zn2L(2)(µ1,5-dca)dca]n (2), [Zn3L(3)2(µ1,5-dca)2]n (3), and [(ZnL(4))2Zn(µ1,5-dca)dca]n (4), have been synthesized using four different Schiff bases L(1)H2 = N,N(/)-bis(3-methoxysalicylidenimino)-1,3-diaminopentane, L(2)H2 = N,N'-bis(5-bromo-3-methoxysalicylidenimino)-1,3-diaminopropane, L(3)H2 = N,N'-bis(5-bromosalicylidenimino)-1,3-diaminopropane, and L(4)H2 = N,N'-bis(5-chlorosalicylidenimino)-1,3-diaminopropane and NaN(CN)2 in order to extend the metal-ligand assembly. The directional properties of linear end-to-end bridging dca ligands have resulted in different metal ion connectivities leading to unique variety of templates in each of the complexes. All the ligands and complexes have been characterized by microanalytical and spectroscopic techniques. The structures of the complexes have been conclusively determined by single crystal X-ray diffraction studies. Thermogravimetric analyses have been performed to investigate the thermal stability of the metal-organic frameworks. Finally, the photoluminescence properties of the complexes as well as their respective ligands have been investigated with a comparative approach.