Conjugated Naphthalenediimide-Pyridinium Salts in Donor-Acceptor Hybrid Materials for Enhanced Photochromic Properties.

As an emerging class of hybrid materials, donor-acceptor (D-A) hybrid crystals with photoactive organic and inorganic components have gradually become an ideal platform for photochromic materials. Wherein the most available organic components are electron-poor naphthalenediimide, pyridinium, and triazine derivatives, inorganic units are electron-rich polyoxometalates and metal halides. Herein, we introduced pyridinium moieties into the naphthalenediimide core by conjugated bonds so as to increase the electron deficiency of organic species for enhanced photochromic properties.

Organic Phosphonium Side-Chain Engineering in Metal Halide Glassy Scintillators for Enhanced X-Ray Dynamic Imaging.

X-ray imaging utilizing organic-inorganic hybrid metal halide (OIHMH) glassy scintillators has garnered significant attention. But their inferior radioluminescence makes achieving rapid image acquisition difficult, posing a persistent challenge for dynamic imaging. Herein, organic phosphonium halide side-chain engineering is proposed, introducing bulky aromatic rings at the alkyl chain ends, to improve the radioluminescence of OIHMHs.

A hot exciton organic glassy scintillator for high-resolution X-ray imaging.

Hot exciton organic scintillators offer promising prospects due to their efficient generation of bright triplet excitons and ultrafast response time, having potential applications in security detection and medical diagnostics. However, fabricating large-area, highly transparent scintillator screens still remains challenging, impeding the realization of high-resolution X-ray imaging. Herein, we firstly demonstrate a novel highly-transparent hot exciton organic glassy scintillator (>87% transmittance @ 450-800 nm), produced using a low-temperature melt-quenching method with 2',5'-difluoro-4,4,4'',4''-tetraphenyl-[1,1':4',1''-terphenyl]-4,4''-diamine (DTPA2F) powder.

Enhanced Stability of Melt-Processable Organic-Inorganic Hybrid Manganese Halides for X-Ray Imaging.

Mn-based metal halides scintillators with high photoluminescence quantum yield (PLQY) have recently emerged as promising large-size candidates for X-ray imaging but still remains as difficult challenge in stability and high processing temperatures. Here, three manganese halides are designed by introducing branched chains into organic cations and extending the carbon chains, namely (i-PrTPP)MnBr, (i-BuTPP)MnBr and (i-AmTPP)MnBr, successfully lowered the melting point of manganese halides to 120.2 °C.

Correction: Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging.

[This corrects the article DOI: 10.1039/D4SC00735B.].

Halogen-bonded charge-transfer co-crystal scintillators for high-resolution X-ray imaging.

The development of high-quality organic scintillators encounters challenges primarily associated with the weak X-ray absorption ability resulting from the presence of low atomic number elements. An effective strategy involves the incorporation of halogen-containing molecules into the system through co-crystal engineering. Herein, we synthesized a highly fluorescent dye, 2,5-di(4-pyridyl)thiazolo[5,4-]thiazole (PyTTz), with a fluorescence quantum yield of 12.

Mechanochemical Synthesis of Cuprous Complexes for X-ray Scintillation and Imaging.

Cuprous complex scintillators show promise for X-ray detection with abundant raw materials, diverse luminescent mechanisms, and adjustable structures. However, their synthesis typically requires a significant amount of organic solvents, which conflict with green chemistry principles. Herein, we present the synthesis of two high-performance cuprous complex scintillators using a simple mechanochemical method for the first time, namely [CuI(PPh)R] (R = 4-phenylpyridine hydroiodide (PH, Cu-1) and 4-(4-bromophenyl)pyridine hydroiodide (PH-Br, Cu-2).

Synthesis, Characterization, and Properties of Sila-Annulated Phenanthrene Imides.

A series of sila-annulated phenanthrene imides were synthesized through a three-step synthetic route, which represent a hybrid class of biphenyl-based π-conjugated molecules incorporating an imide unit and silole. A comprehensive investigation of their structural, photophysical, and electronic properties was studied by experiment and theoretical calculations. Notably, sila-annulated phenanthrene imides with significant aggregation-induced emission (AIE) properties were observed.

Polyoxometalate/-triazine hybrid heterostructures with ultrafast photochromic properties.

As an emerging class of hybrid complexes, donor-acceptor (D-A) hybrid heterostructures, which combine the advantages of both organic and inorganic photoactive components, provide excellent platforms for the fabrication of photochromic materials with enhanced photo-responsive performances. Herein, four novel hybrid heterostructures, namely HTPT·(PWO)·2NMP (1), (HTPT)·(PWO) (2), (HTPT)·(SiWO)·2Cl·2MeCN (3), and HTPT·(HPMoO)·Cl·3NMP (4) (TPT is tri(4-pyridyl)--triazine, NMP is -methylpyrrolidone), have been synthesized and characterized. Benefitting from the strong interactions (anion-π interactions) and matching electron energy levels between the donors and acceptors, some of them exhibited ultrafast photochromic behaviour even up to 1 second.

Naphthalenediimide/Iodobismuthate Hybrid Heterostructures: Water Resistance and Long-Lived Charge-Separated States.

Organic-inorganic hybrid iodobismuthate perovskites have become promising semiconductive materials for their environmentally friendly and light-harvesting characteristics. However, their low-dimensional bismuth-iodide skeletons result in poor charge-separation efficiency, limiting their application in optoelectronic devices. To address this issue, the donor-acceptor (D-A) heterostructures have been introduced to the iodobismuthate hybrid materials by incorporating an electron-deficient ,'-bis(4-aminoethyl)-1,4,5,8-naphthalene diimide (NDIEA) as the electron acceptor and organic counterpart.

Novel Semiconductive Ternary Hybrid Heterostructures for Artificial Optoelectronic Synapses.

Synaptic devices that mimic biological synapses are considered as promising candidates for brain-inspired devices, offering the functionalities in neuromorphic computing. However, modulation of emerging optoelectronic synaptic devices has rarely been reported. Herein, a semiconductive ternary hybrid heterostructure is prepared with a D-D'-A configuration by introducing polyoxometalate (POM) as an additional electroactive donor (D') into a metalloviologen-based D-A framework.

Three Semiconductive 1D Naphthalene Diimide/Iodoplumbate Perovskites with High Moisture Tolerance and Long-Lived Charge Separation States.

Low-dimensional inorganic-organic hybrid perovskites with high moisture tolerance and long-lived charge separation states have captured significant attention in the field of optoelectronic devices. To further achieve the relationship between crystal structures and stability, as well as charge separation behaviors, three one-dimensional hybrid perovskites containing electron-deficient naphthalene diimide ammonium (NDIEA) and electron-rich iodoplumbate chains, [(HNDIEA)PbI]·2DMF (), [(HNDIEA)PbI·(DMF)]·4DMF (), and [(HNDIEA)PbI]·3HO (), were synthesized. Crystal structure determinations revealed various synthesis conditions leading to different stacking modes, especially the inorganic lead iodide fraction, which resulted in different water resistances and charge-separated behaviors.

Guanosine-derived atomically dispersed Cu-N-C sites for efficient electroreduction of carbon dioxide.

Single-atom copper (Cu) embedded within carbon catalysts have demonstrated significant potential in the electrochemical reduction of carbon dioxide (CO) into valuable chemicals and fuels. Herein, we develop a straightforward and template-free strategy for synthesizing atomically dispersed CuNC catalysts (CuG) by annealing the self-assembled guanosine. The CuG catalysts display two-dimensional morphology, tunable pore size and large surface areas that can be adjusted by changing carbonization temperature.

Intramolecular Energy and Solvent-Dependent Chirality Transfer within a BINOL-Perylene Hetero-Cyclophane.

Multichromophoric macrocycles and cyclophanes are important supramolecular architectures for the elucidation of interchromophoric interactions originating from precise spatial organization. Herein, by combining an axially chiral binaphthol bisimide (BBI) and a bay-substituted conformationally labile twisted perylene bisimide (PBI) within a cyclophane of well-defined geometry, we report a chiral PBI hetero-cyclophane (BBI-PBI) that shows intramolecular energy and solvent-regulated chirality transfer from the BBI to the PBI subunit. Excellent spectral overlap and spatial arrangement of BBI and PBI lead to efficient excitation energy transfer and subsequent PBI emission with high quantum yield (80-98 %) in various solvents.

Donor-Acceptor Hybrid Heterostructures: An Emerging Class of Photoactive Materials with Inorganic and Organic Semiconductive Components.

Just as the heterojunctions in physics, donor-acceptor (D-A) heterostructures are an emerging class of photoactive materials fabricated from two semiconductive components at the molecular level. Among them, D-A hybrid heterostructures from organic and inorganic semiconductive components have attracted extensive attention in the past decades due to their combined advantages of high stability for the inorganic semiconductors and modifiability for the organic semiconductors, which are particularly beneficial to efficiently achieve photoinduced charge separation and transfer upon irradiations. In this review, by analogy with the heterojunctions in physics, a definition of the D-A heterostructures and their general design and synthetic strategies are given.

A Three-Component Donor-Acceptor Hybrid Framework with Low-Power X-ray-Induced Photochromism.

Donor-acceptor (D-A) hybrid frameworks with visual X-ray photochromism at room temperature are fascinating because of their promising applications as X-ray detectors. Herein, a 3-fold interpenetrated D-A hybrid framework, [Eu(bcbp)(DMF)(HO)][Co(CN)]·4HO·CHOH (), has been obtained by incorporating electron-rich Co(CN) into the electron-deficient europium viologen framework, which interestingly exhibits ultraviolet and low-power X-ray dual photochromism with a remarkable color change from brown to green. Experimental and theoretical studies revealed that the X-ray photochromic behavior of hybrid could be attributed to its D-A hybrid structural feature increasing the extent of photoinduced electron transfer and thus photogenerated radical species upon X-ray irradiation.

Enantioselective Recognition of Helicenes by a Tailored Chiral Benzo[ghi]perylene Trisimide π-Scaffold.

Enantioselective molecular recognition of chiral molecules that lack specific interaction sites for hydrogen bonding or Lewis acid-base interactions remains challenging. Here we introduce the concept of tailored chiral π-surfaces toward the maximization of shape complementarity. As we demonstrate for helicenes it is indeed possible by pure van-der-Waals interactions (π-π interactions and CH-π interactions) to accomplish enantioselective binding.

Photochromic Polyoxometalate/Perylenediimide Donor-Acceptor Hybrid Crystals with Interesting Luminescent Properties.

The self-assembly of electron-deficient protonated , '-dipyridyltetrachloroperylenediimide (4Cl-DPPDI) and electron-rich polyoxometalate acids HXMO (POMs; X = P or Si; M = W or Mo) resulted in four isomorphous donor-acceptor hybrid crystals - with segregated POM anions and one-dimensional racemic hydrogen-bonded 4Cl-DPPDI networks as electron-donor and -acceptor components, respectively. Because of the compact contacts between the POM anions and 4Cl-DPPDI tectons induced by anion-π interactions, besides enhanced photochromism, these four unique isostructural hybrids exhibited unusual room-temperature phosphorescence (RTP) emissions. More interestingly, owing to the facial compact contacts of two racemic 4Cl-DPPDI tectons induced by lone pair-π-assisted π-π interactions, they also showed unprecedented photon upconversion by triplet-triplet annihilation (TTA).

Photochromic and Room Temperature Phosphorescent Donor-Acceptor Hybrid Crystals Regulated by Core-Substituted Naphthalenediimides.

Donor-acceptor (D-A) hybrid crystals are an emerging kind of crystalline hybrid material composed of semiconductive inorganic donors and organic acceptors. Except for the intrinsic photochromism, recently we have reported that the anion-π polyoxometalate (POM)/naphthalenediimide (NDI) hybrid crystals could produce an interesting room temperature phosphorescence (RTP) quantum yield up to 7.2%.

Donor-Acceptor Conjugated Heptazine Polymers with Highly Efficient Photocatalytic Degradations towards Tetracyclines.

Photocatalysis is an efficient and green technology in the environmental protection. Due to the high charge separation and transfer, donor-acceptor (D-A) conjugated polymers attract much attention for their photocatalytic degradations towards organic pollutants. Herein, the authors reported three novel D-A conjugated polymers, named as HPBP, HPTP, and HPF, with heptazine moieties as electron acceptors, while biphenyl, terphenyl, or fluorene moieties as electron donors, respectively, which indeed exhibit a highly efficient photocatalytic degradation towards tetracyclines upon the visible-light irradiation.

Encapsulating third donors into D-A hybrid heterostructures to form three-component charge-transfer complexes for enhanced electrical properties.

D-A hybrid heterostructures are an emerging class of crystalline hybrid materials composed of semiconductive inorganic donors and organic acceptors. However, due to the steric effects of the inorganic coordination sites, it is difficult for the large organic molecules to form compact packing at the molecular level, resulting in the poor efficiency of photoinduced charge transfers. To achieve an effective carrier separation and transfer, herein we incorporated third donors into a copper(I) halide/thiazolo[5,4-] thiazole D-A heterostructure to construct three novel three-component complexes (Me-PyTTz)CuI·(I) (1), (Me-PyTTz)CuI·(pyrene) (2) and (Me-PyTTz)CuI·(perylene) (3) (PyTTz = 2,5-bis(4-pyridyl) thiazolo[5,4-] thiazole), respectively.

Designing a highly stable coordination-driven metallacycle for imaging-guided photodynamic cancer theranostics.

Coordination-driven self-assembly features good predictability and directionality in the construction of discrete metallacycles and metallacages with well-defined sizes and shapes, but their medicinal application has been limited by their low stability and solubility. Herein, we have designed and synthesized a highly stable coordination-driven metallacycle with desired functionality derived from a perylene-diimide ligand a spontaneous deprotonation self-assembly process. Brilliant chemical stability and singlet oxygen production ability of this emissive octanuclear organopalladium macrocycle make it a good candidate toward biological studies.

Photochromism and photomagnetism in three cyano-bridged 3d-4f heterobimetallic viologen frameworks.

The incorporation of photochromic moieties into coordination polymers is of particular interest because it can endow them with various switching functions such as electrical conductivity, luminescence, and magnetism. In this context, a viologen ligand as a photochromic moiety was incorporated into 3d-4f heterobimetallic hexacyanoferrates, resulting in three novel 3-D photochromic complexes with different metal cations, namely {[Ln(BCEbpy) M(CN) (HO)]·2HO} (denoted as CoDy, CoEu, and FeDy, Ln = Dy, Eu; M = Fe, Co, HBCEbpy·2Br = N,N'-bis(carboxymethyl)-4,4'-bipyridinium dibromide). And the photoresponsive mechanism has been well discussed based on the solid UV-vis, IR, ESR, photoluminescence, and magnetism data.