Near-IR absorbing tetraene-linked π-conjugated porous polymers for energy storage and electrical conductivity.

Tetraene-linked diketopyrrolopyrrole (DPP)-based CMPs were developed Knoevenagel condensation of ditopic active hydrogen containing DPP with tritopic aryl aldehydes. The "tetra-ene" π-arrangement in the molecular framework promotes uninterrupted π-delocalization, resulting in near-infrared (NIR) absorption (∼red edge of 1200 nm), high electrical conductivity in the pristine (10 S m) and doped states (0.2 S m), and moderate energy storage (70 F g).

Vinylene-linked diketopyrrolopyrrole chromophores for electrochromism.

We report a novel series of vinylene-linked DPP compounds (1-5) formed Knoevenagel condensation of dimethyl DPP (6) with various aromatic aldehydes. Incorporating the vinylene linkage and photo- and electro-active groups offered the distinct advantage of extending π-delocalization, resulting in deep-coloured solids with absorption maxima extending to 620-680 nm and low redox potentials. The DPP-triphenylamine compound (5) showed electrochromism in the near-infrared region.

Synthesis of -Azaquinodimethane-based Quinoidal Fluorophores.

Quinoidal π-conjugated systems are sought-after materials for semiconducting applications because of their rich optical and electronic characteristics. However, the analogous fluorescent compounds are extremely rare, with just two reports in the literature. Here, we present the design and development of a third series of quinoidal fluorophores [(2,5-diarylidene)-3,6-bis(hexyloxy)-2,5-dihydropyrazine ()] that incorporates -azaquinodimethane.

Solid-state red-emissive (cyano)vinylene heteroaromatics Pd-catalysed C-H homocoupling.

Thiophene-based π-conjugated systems are important materials for organic electronics; thus, their synthesis is of topical interest. We report fluorescent thiophene/furan-based vinylene and cyanovinylene systems Pd-catalysed homocoupling [Pd(OAc), pivalic acid, KOAc, DMAc, 140 °C]. The methodology is versatile and allows the development of a variety of π-conjugated systems without the need for pre-functionalized building units.

Synthesis of mesoscale ordered two-dimensional π-conjugated polymers with semiconducting properties.

Two-dimensional materials with high charge carrier mobility and tunable band gaps have attracted intense research effort for their potential use in nanoelectronics. Two-dimensional π-conjugated polymers constitute a promising subclass because the band structure can be manipulated by varying the molecular building blocks while preserving key features such as Dirac cones and high charge mobility. The major barriers to the application of two-dimensional π-conjugated polymers have been the small domain size and high defect density attained in the syntheses explored so far.

A Two-Dimensional Poly(azatriangulene) Covalent Organic Framework with Semiconducting and Paramagnetic States.

The black crystalline (aza)triangulene-based covalent organic framework was synthesized from its trinitro-TANG precursor via a one-pot, two-step reaction involving Pd-catalyzed hydrogenation and polycondensation with an aromatic dialdehyde. High crystallinity and permanent porosity of the layered two-dimensional (2D) structure were established. The rigid, electron-rich trioxaazatriangulene (TANG) building block enables strong π-electron interactions manifested in broad absorptions across the visible and NIR regions ( ≈ 1.

Functional π-Conjugated Two-Dimensional Covalent Organic Frameworks.

Fingerprints of π-conjugated compounds are ubiquitous in nature and play a crucial part in human existence. For instance, cis-retinal, an endogenous π-conjugated molecule present in the eye, performs a vital role in the function of visual perception. π-Conjugated molecules have also received a great deal of attention owing to their intriguing optical properties and created a surge in optoelectronics.

Stable Core-Modified Doubly N-Fused Expanded Dibenziporphyrinoids.

We describe one-pot synthesis of stable doubly N-fused expanded dibenziporphyrinoids using readily available precursors under acid-catalyzed conditions. The doubly N-fused expanded dibenziporphyrinoids have been synthesized by adopting an inversion followed by fusion strategy. The studies showed that the dibenziporphyrinoids undergo mono fusion initially, but due to the high stability of doubly fused dibenziporphyrinoids, the monofused macrocycles undergo further fusion to form doubly fused dibenziporphyrinoids.

Construction of Novel Cyclic Tetrads by Axial Coordination of Thiaporphyrins to Tin(IV) Porphyrin.

We report the formation of new cyclic porphyrin tetrads 1 and 2, which were obtained from the reaction between dihydroxytin(IV) porphyrin and cis-dihydroxy-21-thiaporphyrin/21,23-dithiaporphyrin. The unique oxophilicity of tin(IV) porphyrin was the driving force for the formation of these tetrads. Moreover, these novel tetrads represent the first examples of cyclic porphyrins containing tin(IV) that are constructed exclusively on the basis of the "Sn-O" interaction without any other complementary, noncompetitive mode of interactions.

Hybrid Macrocycles of Subporphyrins and Triphyrins.

The dibenzofuran/dibenzothiophene-based nonaromatic hybrid macrocycles, exhibiting the features of both contracted macrocycles, subporphyrins and triphyrins, have been synthesized under simple reaction conditions using readily available precursors. The monoanionic new macrocyclic ligands with three donor atoms, such as two pyrrole nitrogens and one dibenzofuran oxygen or dibenzothiophene sulfur, readily form Re(I) complexes.

Boron complexes of oxasmaragdyrin, a core-modified expanded porphyrin.

We report the synthesis of first examples of BF(2) and B(OR)(2) complexes of oxasmaragdyrin, the expanded core-modified porphyrin, in decent yields under very simple reaction conditions at room temperature. The boron complexation of oxasmaragdyrin alters the electronic properties of the macrocycle significantly as evident by various spectroscopic techniques. Our preliminary studies indicated that the B(OH)(2)-smaragdyrin complex can act as a selective neutral fluoride ion sensor.