The black crystalline (aza)­triangulene-based covalent organic framework TANG-COF 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 (E g ≈ 1.2 eV). The high HOMO energy of TANG-COF (−4.8 eV) enables facile p doping, resulting in electrical conductivity of up to 10–2 S/cm and room-temperature paramagnetic behavior with a spin concentration of ∼10%. DFT calculations reveal dispersion of the highest occupied band both within the 2D polymer layers (0.28 eV) and along their π-stacked direction (0.95 eV).

Red luminescence is found in off-white tris(iodoperchlorophenyl)methane (3I-PTM H) crystals which is characterized by a high photoluminescence quantum yield (PLQY 91 %) and color purity (CIE coordinates 0.66, 0.34). The emission originates from the doublet excited state of the neutral radical 3I-PTM R , which is spontaneously formed and becomes embedded in the 3I-PTM H matrix. The radical defect can also be deliberately introduced into 3I-PTM H crystals which maintain a high PLQY with up to 4 % radical concentration. The immobilized iodinated radical demonstrates excellent photostability (estimated half-life > 1 year under continuous irradiation) and intriguing luminescent lifetime (69 ns). TD-DFT calculations demonstrate that electron-donating iodine atoms accelerate the radiative transition while the rigid halogen-bonded matrix suppresses the nonradiative decay.

We here report the synthesis of a new class of carbohydrate-based block copolymers, poly(3-hexylthiophene)-block-peracetylated maltoheptaose (P3HT-b-AcMal 7 ) and poly(3-hexylthiophene)-block-maltoheptaose (P3HT-b-Mal 7 ), and their bulk and self-assembled thin films morphological characterizations by atomic force microscopy, transmission electron microscopy, and small-angle X-ray scattering. The block copolymers were synthesized via copper(I)-catalyzed 1,3-dipolar azide−alkyne cycloaddition of azido-functionalized AcMal 7 and end-functionalized P3HT with alkyne group prepared by modified Grignard metathesis polymerization, followed by deacetylation of the AcMal 7 block. The half-pitch of sub-10 nm scale lamellar structures, one of the smallest domain sizes of microphase separated block copolymers reported to date, was self-organized in the bulk and thin films of P3HT-b-AcMal 7 by thermal annealing above the melting temperature of the P3HT segment. Meanwhile, thermodynamic microphase separation of P3HT-b-Mal 7 was restricted due to strong inter-and intrachain hydrogen bonding among the hydroxyl groups of the Mal 7 block, which was confirmed by an in situ stepwise heating and cooling Fourier transform infrared spectroscopy study.

After ushering in a new era of technological developments in data computation and electronics, the focus has shifted toward more efficient and faster computing and processing components. This drives the production boost of stateof-the-art electronics with a low product lifecycle. The disposal of electronic wastes has imposed a significant environmental impact on the planet; therefore, researchers have been searching for alternative materials to replace conventional silicon-based electronics without compromising performance. [1][2][3] With regard to the growing interest in environmental protection, the feasibility of using recycled and biobased materials to develop renewable polymers and their component integration into electronic devices has gradually garnered increasing attention in the past decades. [4,5] Current synthetic approaches enable the tailoring of biobased molecules and their bioderived polymers inspired by their biological counterparts at different scales and customization of multifunctional properties and performances with biodegradability, thereby, significantly enriching the implementation of biocompatible green electronics, including artificial skin and wearable neuromorphic, in information storage systems. Several novel memory device architectures using various types of biobased materials, including proteins, polysaccharides, ribonucleic acid, deoxyribonucleic acid, and viruses, have been developed for use in electronic devices. [6][7][8][9][10][11][12][13][14] Among them, renewable polysaccharides, including cellulose, starch, and chitin, are widely used as building blocks for bioderived materials in the development of green memory devices. [15][16][17][18][19][20][21] For instance, Chiu et al. reported a pentacene-based three-terminal transistor memory using oligosaccharide maltoheptaose as the dielectric layer to demonstrate an electrically bistable memory device under electrical programming/erasing operations using a gate electrode. [22] However, conventional voltage-driven memory devices, which are used in von Neumann computing systems, lag far behind the Owing to ever-increasing environmental impact, nature-inspired biomimetic electronics are key to unlock the potential of developing environmentally friendly brain-like computing and biomimetic artificial-intelligence systems. Thus far, the development of photosynaptic devices via green processing using biobased materials has become a major challenge, owing to restrictions in complex architecture, material design, and stimulation wavelength. This article reports on the first bioinspired phototransistor using biocomposites comprising semiconducting block copolymers, poly(3-hexylthiophene)-blockmaltoheptaose, and bacteriochlorophyll (BCHL), which extend the photoresponse from visible to UV to near-infrared light, to exhibit fundamental sensing, computing, and memory functions. The superior ultrafast (50 ms) and multilevel (>9 bits) photoresponses of a single cell of the synaptic devices are attributed to hydrogen-bonding interaction (i) betwe...