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Dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) is a widely used small-molecular p-type organic semiconductor. Despite the broad availability of high-performance DNTT transistors, there is a lack of investigation into other devices based on this semiconductor. In this study, rectifying diodes with DNTT as a single transport medium are fabricated and characterized. Realizing unipolar current rectification from asymmetric metal contacts, a number of physical and electrical properties of DNTT are made accessible. Current–voltage measurement, broad-band impedance spectroscopy, drift-diffusion simulation, and equivalent-circuit modeling are combined to quantify important parameters such as dielectric constant, trap energy, and lifetime. These results provide a practical reference for the design and optimization of diverse electronic devices incorporating DNTT. [ABSTRACT FROM AUTHOR]

The vibronic structure and nuclear dynamics in the first five excited singlet electronic states of bithiophene (2T) are investigated here. Specifically, considerations are given to comprehend the first two structureless and broad electronic absorption bands and the role of nonadiabatic coupling in the excited state relaxation mechanism of 2T in the gas phase. Associated potential energy surfaces (PESs) are established by constructing a model vibronic coupling Hamiltonian using 18 vibrational degrees of freedom and extensive ab initio electronic structure calculations. The topographies of these PESs are critically examined, and multiple conical intersections are established. The nuclear dynamics calculations are performed by propagating wave packets on the coupled electronic manifold. The present theoretical results are in good agreement with the experimental observations. It is found that strong nonadiabatic coupling between the S1–S4 and S1–S5 states along totally symmetric modes is predominantly responsible for the structureless and broad first absorption band, and overlapping S2, S3, S4, and S5 states form the second absorption band. Photorelaxation from the highly excited S5 to the lowest S1 state takes place through a cascade of diabatic population transfers among the S1–S4–S5 electronic manifold within the first ∼100 fs. Totally symmetric C=C stretching, C–S stretching, C–H wagging, ring puckering, and inter-ring bending modes collectively drive such relaxation dynamics. [ABSTRACT FROM AUTHOR]

Taking into account the electron-rich and visible light response of thiophene, first-principles calculations have been carried out to explore the photocatalytic activity of donor–acceptor polymers incorporating thiophene and boron. Honeycomb-kagome boron–thiophene (BTP) polymers with varying numbers of thiophene units and fixed B center atoms are direct bandgap semiconductors with tunable bandgaps ranging from 2.41 to 1.88 eV and show high absorption coefficients under the ultraviolet and visible regions of the solar spectrum. Fine-tuning the band edges of the BTP polymer is efficiently achieved by adjusting the pore size through the manipulation of thiophene units between the B centers. This manipulation, achieved without excessive chemical functionalization, facilitates the generation of an appropriate quantity of photoexcited electrons and/or holes to straddle the redox potential of the water. Our study demonstrates that two units between B centers of thiophene in BTP polymers enable overall photocatalytic water splitting, whereas BTP polymers with larger pores solely promote photocatalytic hydrogen reduction. Moreover, the thermodynamics of hydrogen and oxygen reduction reactions either proceed spontaneously or need small additional external biases. Our findings provide the rationale for designing metal-free and single-material polymer photocatalysts based on thiophene, specifically for achieving efficient overall water splitting. [ABSTRACT FROM AUTHOR]

Catalysis with engineered enzymes has provided more efficient routes for the production of active pharmaceutical agents. However, the potential of biocatalysis to assist in early-stage drug discovery campaigns remains largely untapped. In this study, we have developed a biocatalytic strategy for the construction of sp3-rich polycyclic compounds via the intramolecular cyclopropanation of benzothiophenes and related heterocycles. Two carbene transferases with complementary regioisomer selectivity were evolved to catalyse the stereoselective cyclization of benzothiophene substrates bearing diazo ester groups at the C2 or C3 position of the heterocycle. The detailed mechanisms of these reactions were elucidated by a combination of crystallographic and computational analyses. Leveraging these insights, the substrate scope of one of the biocatalysts could be expanded to include previously unreactive substrates, highlighting the value of integrating evolutionary and rational strategies to develop enzymes for new-to-nature transformations. The molecular scaffolds accessed here feature a combination of three-dimensional and stereochemical complexity with rule-of-three properties, which should make them highly valuable for fragment-based drug discovery campaigns.

Integration of spirocycles with buckybowls is a promising strategy to construct three‐dimensional (3D) curved π‐systems and to endow distinctive physicochemical features arising from buckybowls. Herein, a series of carbon‐bridged spiro‐type heterosumanenes (spiro‐HSEs) were synthesized by combining 9,9′‐spirobifluorene and dichalcogenasumanenes (DCSs). It is found that spiro‐conjugation plays an important role in the geometric and electronic structures of spiro‐HSEs. The bowl depth of DCSs moiety becomes larger in the spiro‐HSEs. Owing to the Jahn‐Teller (J‐T) effect, two DCSs segments of spiro‐HSEs have different bowl depths accompanied with the unequal distribution of charge in radical cation state. Taking advantage of the typical reactions of DCSs, selective transformations of spiro‐HSEs have been adopted in accordance to the nature of chalcogen atoms (S, Se, Te) to bestow the value‐added functionalities. The emissive property is enhanced by converting the thiophene rings of S‐doped spiro‐HSE into thiophene S,S‐dioxides. A chiroptical polycycle could be produced by ring‐opening of the edge benzene of Se‐doped spiro‐HSE. The covalent adduct of Te‐doped spiro‐HSE with Br2 forms non‐centrosymmetric halogen‐bonded networks, resulting in the high performance second‐order nonlinear optics (NLO). [ABSTRACT FROM AUTHOR]

To address the high‐cost issue that impedes the large‐scale fabrication and industrialization of organic solar cells (OSCs), it is crucial to design low‐cost photovoltaic materials with simplified synthesis procedures. In this study, a novel fully non‐fused acceptor, ATVT‐BO, featuring a triisopropylbenzene‐substituted (E)‐1,2‐di(thiophen‐2‐yl)ethene (TVT) unit as the central core is designed and synthesized. A control acceptor, A4T‐BO, with the same alkyl chains but a bithiophene central core, is also synthesized for comparison. Theoretical calculations and practical measurements reveal that compared to A4T‐BO, the insertion of an ethylene bond in ATVT‐BO enhances the molecular planarity and reduces the aromaticity, leading to enhanced π‐electron delocalization and thus improved electron mobility and a red‐shifted optical absorption spectrum. The 3D molecular packing mode of ATVT‐BO, characterized by tight intermolecular interactions, also promotes efficient charge transport in OSCs. Consequently, when paired with the low‐cost polymer PTVT‐T, featuring an ester‐substituted TVT structure, as the photoactive layer, the PTVT‐T:ATVT‐BO‐based device achieves a remarkable power conversion efficiency of 14.8%, distinctly higher than that of PTVT‐T:A4T‐BO‐based cell. The result highlights the significant potential of TVT units in creating both low‐cost polymer donors and fully non‐fused acceptors, which opens up new possibilities for designing low‐cost photoactive materials in OSCs. [ABSTRACT FROM AUTHOR]

The new halogen‐free donor polymer PCN6 is constructed using 2‐ethylhexyl‐4,6‐dibromo‐3‐cyano‐thieno[3,4‐b]thiophene as acceptor (A) block, and is compared in detail with the commercially available PTB7‐Th. It is found that PCN6 has a wider film absorption (300–700 nm) and lower highest occupied molecular orbital (HOMO) energy levels (−5.52 eV) than PTB7‐Th (−5.34 eV), suggesting a great advantage of the monocyano‐functionalized modification strategy in terms of molecular absorption and energy level tuning. The performance difference between PCN6:Y6‐ and PTB7‐Th:Y6‐based organic solar cells (OSCs) is compared by a series of studies including light intensity dependence, carrier mobility, AFM, TEM, and GIWAXS. The results show that PCN6:Y6‐based OSCs have stronger crystallinity, better charge transport, higher and more balanced carrier mobility, and less exciton complex loss. Therefore, the power conversion efficiency (PCE) of PCN6:Y6‐based OSCs reaches 11.34%, while the PCE of PTB7‐Th:Y6‐based OSCs is only 9.02%. These results suggest that 2‐ethylhexyl‐4,6‐dibromo‐3‐cyano‐thieno[3,4‐b]thiophene is an excellent A block for the construction of halogen‐free donor polymers with low HOMO energy levels, and also demonstrate that the introduction of cyano in the conjugated backbone of polymers is a good strategy to achieve high‐performance OSCs. [ABSTRACT FROM AUTHOR]

We report the C–F bond heteroarylation of trifluoromethylarenes with heteroarenes by using Ir(ppy)3 catalyst and Bu3 SnI under visible-light irradiation. Various heteroarenes such as pyrrole, furan, and thiophene derivatives were applied to the present reaction. The present heteroarylation enables the transformation of various functionalized trifluoromethylarenes because of the mild reaction conditions. Notably, the late-stage transformation of a drug molecule, bicalutamide, was demonstrated. Mechanistic studies including a light on–off interval experiment, Stern–Volmer luminescence-quenching measurements, and DFT calculations clarified two critical roles of Bu3 SnI for the successful progress of the heteroarylation. Bu3 SnI functions as a fluoride ion scavenger to suppress the undesired C–F bond re-formation. Bu3 SnI also acts as a single-electron source for the reduction of photoexcited Ir(ppy)3 * to generate Ir(II) species to effectively reduce ArCF3. [ABSTRACT FROM AUTHOR]

As one of the most potential platforms for heterogeneous catalysis, two‐dimensional porphyrin‐based covalent organic frameworks (COFs) have attracted great research interests. In this work, following the correlation of COF structure and their performance, a type of donor–acceptor 2D COF (Por‐COF‐Zn) based on porphyrin and thiophene units was designed and easily constructed by one‐pot method using 5,10,15,20‐tetra‐(4‐aminophenyl)porphyrin (TAPP), thieno[3,2‐b]thiophene‐2,5‐dicarbaldehyde, and zinc acetate. The as‐synthesized COF material is tested to show high crystallinity and good thermal and chemical stability. The Brunauer–Emmett–Teller (BET) measure results show that the specific surface area of Por‐COF‐Zn is 413.6 m2g−1, and the pore volume is 0.279 cm3g−1. Transient photocurrent response and EIS measurement also demonstrate that Por‐COF‐Zn exhibits an efficient separation of photogenerated electron/hole pairs. The photocatalytic performance of the resulted COF was further evaluated by using intramolecular cyclization of N‐phenyl‐o‐phenylenediamine and benzaldehyde to form benzimidazole derivative. The catalyst system exhibited good to high conversion efficiency, moderate substrate applicability, and excellent stability and recyclability for the catalytic cyclization approach of benzimidazoles. The catalytic mechanism should be contributed to the synergistic effect of organic framework and metallic zinc. Our current work also provides valuable information for understanding COF‐based photocatalytic systems and further highlight new insights to meet new challenges of heterogeneous photocatalysis. [ABSTRACT FROM AUTHOR]

Two new copolymers (named PTO‐BO and PTO‐HD) with alkyloxime‐substituted thiophene (TO) as acceptor unit and 6‐undecylthiopheno[3,2‐b]thiophene spacer as π‐bridge were synthesized and applied in organic solar cells (OSCs) as electron donors. PTO‐HD with 2‐hexyldecyl side chains on TO moiety possesses more suitable phase separation, more efficient exciton dissociation and charge transportation, and less charge recombination than PTO‐BO with 2‐butyloctyloxime‐substituted thiophene in OSCs with Y6 as the acceptor. As a result, the OSCs based on PTO‐HD:Y6 achieved an optimal power conversion efficiency (PCE) of 13.89% with a Voc of 0.799 V, a Jsc of 22.74 mA cm−2, and a FF of 67.67% without additives, which is higher than that (12.29%) of PTO‐BO:Y6 OSCs. [ABSTRACT FROM AUTHOR]

ABSTRACT In this study, we report the synthesis, characterization, and biological investigation of antimony(III) halide complexes with various coordination architectures constructed from thiophene thiosemicarbazones. Antimony(III) thiophene‐2‐carbaldehyde thiosemicarbazone complexes (1, 2, 4, and 5) exhibit a square pyramidal geometry, with ligands coordinated to the central antimony atom in two distinct binding modes. In contrast, antimony(III) 2‐acetylthiophene thiosemicarbazone complexes (3, 6, and 7) adopt a seesaw geometry. These complexes (1–7) represent the first reported examples of antimony(III) halide thiosemicarbazone compounds. The unique coordination environments observed in these complexes are of significant importance within the realm of antimony chemistry. These synthesized complexes exhibit different coordination geometries as well as potential biological activities. The antiproliferative activity against the human breast adenocarcinoma (MCF‐7) cell line and antimicrobial activity against Gram‐positive and Gram‐negative bacteria were assessed. Antimony(III) thiophene‐2‐carbaldehyde thiosemicarbazone complexes (1, 2, 4, and 5) showed significant antiproliferative activity with IC50 values ranging from 8.5 to 19.1 μM, while antimony(III) 2‐acetylthiophene thiosemicarbazone complexes (3, 6, and 7) had higher IC50 values. Additionally, the antimony complexes demonstrated selective antimicrobial activity against Gram‐negative bacteria. [ABSTRACT FROM AUTHOR]

Dithieno[3,2‐b:2',3'‐d]thiophene (DTT) derivative contains three annulated thiophene rings, which have attracted great attention in the field of materials due to its planar and conjugated molecular, structural rigidity, and increased solubility. Herein, the one‐step modular construction of a series of structurally well‐defined 2,6‐disubstituted dithieno[3,2‐b:2',3'‐d]thiophenes (2,6‐DTT) involves Pd/Cu(I)‐catalyzed Sonogashira coupling and LiNH2‐mediated ring‐closing reaction with element sulfur was reported. The method allows the selective and straightforward introduction of different aryl substitution into DTT without otherwise tedious separation and purification processes. The preliminary study of the thermal and photophysical properties demonstrated that the introduction of substituent in phenyl has great impact for the parent molecule, which enable this protocol to synthesis high‐performance 2,6‐DTT through the different alkynes. [ABSTRACT FROM AUTHOR]

Incorporation of a thieno[3,2‐b]thiophene into an isophlorinoid‐like framework alters the aromaticity by extending the macrocyclic π‐circuit. Their opto‐electronic and aromatic properties significantly differ from other 22π and 34π porphyrinoids. Among the three different 34π hexaphyrins, furan based hexaphyrin adopts a non‐aromatic ‘figure‐of‐eight’ conformation. Replacing all the furans either by thiophene or selenophene induces a planar conformation with aromatic characteristics. Spectro‐electrochemical studies revealed reversible two‐electron ring oxidation to yield their 4nπ dicationic species respectively. [ABSTRACT FROM AUTHOR]

Breaking aromaticity by inserting additional atoms within the skeleton of heteroaromatic rings has gained significant attention over the years. As part of the emerging concept of 'skeletal editing', this short review retraces the recent progress made on dearomative enlargement reactions of both five- and six-membered heterocycles. 1 Introduction 2 Dearomative Enlargement of Five-Membered Rings 2.1 Pyrroles, Furans, Thiophenes and Their Fused Analogues 2.2 Pyrazoles, Isoxazoles, Isothiazoles and Their Fused Analogues 3 Dearomative Enlargement of Six-Membered Rings 4 Conclusion and Perspectives [ABSTRACT FROM AUTHOR]

Low‐band gap semiconductor polymer materials play a crucial role in the field of organic optoelectronics. In this context, a series of low‐band gap polymers containing thienopyrazine as the acceptor and cyclofluorene–bithiophene as the donor were synthesized and utilized in resistive random access memory (RRAM) devices. These memory devices consistently exhibit nonvolatile flash memory behavior. Remarkably, all three polymers demonstrate stability even after 1000 cycles without significant fluctuations. Notably, the three polymer‐based devices also exhibit excellent ternary memory performance, with current ratios of 1:102.8:104, 1:101.3:103.9, and 1:101.8:103.6. Furthermore, the photoelectric properties of the three polymers and the conduction mechanisms of the memory devices were thoroughly discussed. [ABSTRACT FROM AUTHOR]

Here in, we have designed two new unfused non‐fullerene small molecules using asymmetric benzo[1,2‐b:3.4‐b′, 6,5‐b”]trithiophene (BTT) as the central donor core and different terminal units i. e., 2‐(3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile (NFA‐4) and 1,3‐diethyl‐2‐thioxodi hydropyrimidine‐4,6 (1H,5H)‐dione (NFA‐5) and examined their optical and electrochemical properties. Using a wide band‐gap copolymer D18, organic solar cells (OSCs) based on bulk heterojunction of D18:NFA‐4 and D18:NFA‐5 showed overall power conversion efficiency (PCE) of about 17.07 % and 11.27 %, respectively. The increased PCE for the NFA‐4‐based OSC, compared to NFA‐5 counterpart, is due higher value of short circuit current (JSC), open circuit voltage (VOC), and fill factor (FF). Following the addition of small amount of NFA‐5 to the binary bulk heterojunction D18:NFA‐4, the ternary organic solar cells attained a PCE of 18.05 %, surpassing that of the binary counterparts due to the higher values of which is higher than that for the binary counterparts and attributed to the increased values of JSC, FF, and VOC. The higher value of JSC is linked to the efficient use to excitons transferred from NFA‐5 to NFA‐4 with a greated dipole moment than NFA‐5 and subsequently dissociated into a free charge carrier efficiently. [ABSTRACT FROM AUTHOR]

A comprehensive investigation of two new molecular triads incorporating the diketopyrrolopyrrole unit into a quinoidized thienothiophene skeleton, which is further end‐capped with dicyanomethylene (DPP‐TT‐CN) or phenoxyl groups (DPP‐TT‐PhO), has been carried out. A combination of UV‐Vis‐NIR and infrared spectroelectrochemical techniques and cryogenic UV‐Vis‐NIR absorption spectroscopy supported by theoretical calculations has been used. The main result is the formation of similar H‐aggregates in the dimerization process of the neutral molecules and of the charged anionic species. The experimental absorption spectra of the aggregated species are accurately reproduced by quantum chemical calculations using the Spano's model, including excitonic coupling for the dimeric forms and full vibronic resolution of the absorption bands. The strong excitonic coupling taking place is key to understand the electronic structure of the dimeric species and has been instrumental to disentangle the type of H‐aggregation. This study is of relevance to get a better understanding of the molecular aggregation of organic π‐conjugated chromophores and is useful as a guideline for the refinement of the engineering of molecular materials for which supramolecular design is required. [ABSTRACT FROM AUTHOR]

Carbazole‐based self‐assembled molecules (SAMs) are widely applied in inverted perovskite solar cells (iPSCs) due to their unique molecular properties. However, the symmetrical structure of the carbazole‐based SAMs makes it difficult to finely regulate their performance, which impedes the further enhancement of the efficiency and stability of iPSCs. This work demonstrates that by constructing an asymmetric carbazole core, 9H‐thieno[2′,3′ : 4,5]thieno[3,2‐b]indole) (TTID), the key properties of SAM molecules can be effectively regulated. It has been confirmed that the hybrid thieno[2,3‐b]thiophene unit of this asymmetric core governs the energy level, the surface wettability, and the defect passivation capability of the SAMs, while the substituent of core has a greater impact on the molecular dipole and device stability. The synergistic effects from thieno[2,3‐b]thiophene and fluorine lead to the KF‐derived iPSC demonstrating a certified power conversion efficiency (PCE) of 25.17 % and excellent operational stability. This hybrid design concept offers a promising approach for the further structural modification of SAMs in iPSCs. [ABSTRACT FROM AUTHOR]

A library of neutral and cationic palladium complexes of cis‐chelating hetero‐dicarbene ligands have been prepared. These ligands contain two different NHC donors allowing for a wider degree of variation, and the impact of the distinct NHC units has been compared using various spectroscopic means. In addition, the catalytic activities of these complexes in the direct C‐H arylation of thiophenes with aryl halides were studied leading to the finding that the neutral dibromido complexes of the type [PdBr2(diNHC)] generally outperformed their cationic [Pd (NCMe)2(diNHC)](OTf)2 counterparts. More importantly, complexes containing more distinct NHC units give rise to superior catalysts due to an amplified "stereoelectronic asymmetry" within the complex. A preliminary photophysical study of some selected thiophene reaction products has been conducted as well. The ability to individually change each NHC donor in such dicarbene ligands allows for a better fine‐tuning of complex properties in search for superior catalysts. [ABSTRACT FROM AUTHOR]

Achieving high electrical conductivity (σ) and power factor (PF) simultaneously remains a significant challenge for n‐type organic themoelectrics (OTEs). Herein, we demonstrate the state‐of‐the‐art OTEs performance through blending a fused bithiophene imide dimer‐based polymer f‐BTI2g‐SVSCN and its selenophene‐substituted analogue f‐BSeI2g‐SVSCN with a julolidine‐functionalized benzimidazoline n‐dopant JLBI, vis‐à‐vis when blended with commercially available n‐dopants TAM and N‐DMBI. The advantages of introducing a more lipophilic julolidine group into the dopant structure of JLBI are evidenced by the enhanced OTEs performance that JLBI‐doped films show when compared to those doped with N‐DMBI or TAM. In fact, thanks to the enhanced intermolecular interactions and the lower‐lying LUMO level enabled by the increase of selenophene content in polymer backbone, JLBI‐doped films of f‐BSeI2g‐SVSCN exhibit a unprecedent σ of 206 S cm−1 and a PF of 114 μW m−1 K−2. Interestingly, σ can be further enhanced up to 326 S cm−1 by using TAM dopant as a consequence of its favorable diffusion behavior into densely packed crystalline domains. These values are the highest to date for solution‐processed molecularly n‐doped polymers, demonstrating the effectiveness of the polymer‐dopant matching approach carried out in this work. [ABSTRACT FROM AUTHOR]

Visible light-responsive antimicrobial coatings are of importance for antibacterial applications owing to widespread multidrug-resistant infections. Herein, the photocatalytic disinfection performance of an all-organic poly[2,11′-thiophene-ethylene-thiophene-alt-(2,5-(3-carboxyl)-thiophene] (PTET-T-COOH)/polyurethane (PU) coating was synthesized and evaluated. The coating consists of both a protective PU layer and a photoactive layer (PTET-T-COOH), which was prepared using isocyanate groups as linkers, then fabricated by drop-casting. The chemical linkage between PTET-T-COOH and NCO-terminated PU was researched based on ATR-FTIR and XPS analyses. The developed coating demonstrated good photocatalytic bactericidal performance on S. aureus under visible-light irradiation for 6 h. This study provided an effective platform for fabricating environmental-friendly and cheap antimicrobial surfaces. [ABSTRACT FROM AUTHOR]

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The isoindigo and its derivatives have rapidly garnered attention as widely employed electron‐deficient moieties, finding extensive applications in organic field‐effect transistors. In this study, four different isoindigo‐based organic semiconductor polymers were synthesized via a Stille coupling reaction of four isoindigo molecules with varying side chains serving as acceptors and bithiophene as donors. Furthermore, their optical, electrochemical, thermal stability, and other relevant properties were comprehensively evaluated. These polymers exhibited remarkable electrochemical and thermal stability attributed to their low LUMO energy level, which facilitates effective electrical contact between the semiconductor layer and the source/drain while ensuring excellent air stability for the semiconductor polymers. Additionally, solution‐gate field‐effect transistors prepared using these polymers achieved hole mobilities of 10−2 cm2 V−1 S−1 along with an Ion/Ioff ratio of 8.39×103, demonstrating exceptional field‐effect performance. [ABSTRACT FROM AUTHOR]

In the commercial development of perovskite solar cells, the main challenge lies in achieving efficient devices with high stability. Additive engineering in polycrystalline perovskites is considered as an effective approach to address this challenge by passivating surface defects and reducing carrier losses associated with these defects. In this work, the passivation effect of molecules with different side chain groups on perovskites and the role of binding energy in mitigating carrier loss are studied. The findings reveal that the thiophene group is particularly effective in passivating defects and enhancing hole transport. Consequently, devices treated with 2‐thienylmethylamine hydrochloride (TMAC) demonstrate a champion power conversion efficiency (PCE) of 24.63%. Furthermore, these TMAC‐treated devices exhibit remarkable stability, maintaining over 93.13% of their initial efficiencies after 1200 h of continuous illumination under maximum power point tracking (MPPT). This research presents a pathway to enhance the optoelectronic performance and stability of perovskite solar cells. [ABSTRACT FROM AUTHOR]

Various indoles undergo Friedel–Crafts alkylation at the 3-position when treated with secondary arylmethyl acetates in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) and 2,6-lutidine. Tertiary benzylic alcohols are also effective alkylating agents, undergoing TMSOTf-promoted activation to yield alkylated indoles that feature quaternary centers. A related study shows that benzofuran reacts under similar conditions to yield 2-alkylated benzofurans when treated with similar alkylating agents, and the reaction has been extended to include other representative heteroarenes. Yields for these Friedel–Crafts alkylation products range from 43%–99% over a wide range of substrate combinations. [ABSTRACT FROM AUTHOR]

The development of adsorbent materials for highly efficient iodine capture is in high demand from the perspective of ecological environment and human health. Herein, two covalent organic frameworks (COFs), JLNU-312 and JLNU-313, were successfully synthesized for iodine adsorption. The obtained JLNU-COFs possess high crystallinity and one-dimensional mesoporous channels. Iodine adsorption experiments demonstrated that both COF materials exhibit effective performance for iodine adsorption, with a maximum amount of up to 4.67 g g−1 for JLNU-312 and 2.47 g g−1 for JLNU-313. Moreover, both JLNU-COFs have good stability, reusability and iodine retention capacity. Theoretical calculations clearly show that the higher adsorption performance of JLNU-312 is also due to the strong interaction between the adsorbed iodine and the abundant triazine nitrogen-rich adsorption sites uniformly distributed in the pore. This work shows that effective iodine adsorbents can be achieved by introducing nitrogen-rich sites into the framework of COF materials. [ABSTRACT FROM AUTHOR]

Novel porphyrin(2.1.2.1) Pd(II) complexes with various aromatic π rings (benzo, naphthalene and thiophene) embedded between dipyrrin units have been synthesized. Their molecular structures and optical and electronic properties were confirmed and fully investigated. These Pd(II) complexes showed moderate to good capacity of singlet oxygen generation under light irradiation. [ABSTRACT FROM AUTHOR]

The operational stability becomes a key issue affecting the commercialization for organic field-effect transistors (OFETs). It is widely recognized to be closely related to the defects and traps at the interface between dielectric and organic semiconductors, but this understanding does not always effectively address operational instability, implying that the factors influencing the operational stability have not been fully understood. Here, we reveal that the self-heating effect is another crucial factor in operational stability. By using hexagonal boron nitride (hBN) to assist interfacial thermal dissipation, the dinaphtho[2,3-b: 2',3'-f] thieno[3,2-b] thiophene (DNTT) FETs exhibit high mobility of 14.18 cm2 V-1 s-1 and saturated power density up to 1.8 × 104 W cm-2. The OFET can operate at a power density of 1.06 × 104 W cm-2 for 30,000 s with negligible performance degradation, showing excellent operational stability under high power density. This work deepens the understanding on operational stability and develops an effective way for ultrahigh stable devices. [ABSTRACT FROM AUTHOR]

1-(3-Methylthiophen-2-yl)-N-(3,4,5-trimethoxyphenyl)methanimine (1, MTM) was synthesized from 3-methylthiophene-2-carbaldehyde and 3,4,5-trimethoxyaniline and characterized by FTIR and 1H and 13C NMR spectra. The geometric structure of the title compound was optimized, and its electronic (FMO, NLO, MEP, NBO), spectroscopic (NMR, IR, UV), and thermodynamic properties were calculated by quantum chemicial methods. The calculated and experimental geometric parameters were compared with each other. Compound 1 was tested for leishmanicidal activity against Leishmania infantum by the broth microdilution method and was found to be efficient against Leishmania infantum promastigotes in the concentration range studied. Possible interactions responsible for the antileishmanial activity were determined by molecular docking analysis against trypanothione reductase (TRe). The docking results demonstrated high inhibition constant of the title compound and supported its antileishmanial activity. [ABSTRACT FROM AUTHOR]

Synthesis of N-substituted 4-aryl-2-(3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophen-2-ylamino)-4-oxobut-2-enamides by the reaction of the substituted 2-[(5-aryl-2-oxofuran-3(2H)-ylidene)amino]-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitriles with primary amines was developed. Anti-inflammatory activity and acute toxicity of the synthesized compounds were examined. It was found that the synthesized compounds possess pronounced anti-inflammatory activity and low toxicity. According to the classification of toxicity of drugs, the synthesized amides belong to toxicity class V of practically nontoxic substances. [ABSTRACT FROM AUTHOR]

This study reports the successful design and synthesis of two novel polymerized nonfused ring electron acceptors, P-2BTh and P-2BTh-F , derived from the high-performance nonfused ring electron acceptor, 2BTh-2F. Prepared via Stille polymerization, these polymers feature thiophene and fluorinated thiophene as π-bridge units. Notably, P-2BTh-F , with difluorothiophene as the π-bridge, exhibits a more planar backbone and red-shifted absorption spectrum compared with P-2BTh. When employed in organic solar cells (OSCs) with PBDB-T as the donor material, P-2BTh-F -based devices demonstrate an outstanding power conversion efficiency (PCE) of over 11%, exceeding the 8.7% achieved by P-2BTh -based devices. Furthermore, all-polymer solar cells utilizing PBDB-T: P-2BTh-F exhibit superior storage stability. Additionally, P-2BTh-F was explored as a functional additive in a high-performance binary system, enhancing stability while maintaining comparable PCE (19.45%). This strategy offers a cost-effective approach for fabricating highly efficient and stable binary and ternary organic solar cells, opening new horizons for cost-effective and durable solar cell development. [ABSTRACT FROM AUTHOR]

New triheteroyclic compounds containing quinazolinone, thiophene, andthiadiazole /thiazolidinone structureswere synthesized and characterized by FT-IR, 1H–NMR, and13C–NMRspectral data. The new compounds' inhibitory activities on urease and acetylcholinesterase were assessed. All triheterocyclic compounds with thiadiazole ring have urease and acetylcholinesteraseinhibitory activities.Especially compound 5a; 3-[(5-(phenylamino)-1,3,4-thiadiazol-2-yl]methyl-2-(thiophen-3-ylmethyl)quinazolin-4(3H)-onehas the best urease inhibition result with 13.30 ± 0.15 µg/mL IC50 value, and it also has the best acetylcholinesterase inhibition with 20.30 ± 0.15 µg/mL IC50 value. [ABSTRACT FROM AUTHOR]

In this work, the adsorption of thiophene on the Mg4O4 cluster was examined at the LC-ωPBE/6-311G(d,p) level of theory. The influence of replacing hydrogen atoms of thiophene with fluorine atoms was considered. The comparison of relative stabilities of possible isomers indicated most stable isomers were 3-FT ... Mg4O4, 3,4-DFT ... Mg4O4, 2,3,4-TFT ... Mg4O4 structures in the mono, di and tri-fluorinated thiophenes, respectively. Corrected adsorption energy and thermodynamic parameter values of these systems were evaluated and the substituent effect on the adsorption was explored. 2-FT ... Mg4O4, 3,4-DFT ... Mg4O4, 2,3,4-TFT ... Mg4O4 structures indicated the most significant adsorptions in the mono, di and tri-fluorinated thiophenes, respectively. Electrophilicity-based charge transfer (ECT) was employed to illustrate charge transfer between aromatic systems and the Mg4O4 cluster. Quantum theory of atoms in molecule (QTAIM) and interaction region indicator (IRI) were used to deeply investigate two fragments. [ABSTRACT FROM AUTHOR]

In the present study, we prepared new sixteen different derivatives. The first series were prepared (methylene)bis(2-(thiophen-2-yl)-1H-indole) derivatives which have (indole and thiophene rings) by excellent yield from the reaction (2 mmol) 2-(thiophen-2-yl)-1H-indole and (1 mmol) from aldehyde. The second series were synthesized (2-(thiophen-2-yl)-1H-indol-3-yl) methyl) aniline derivatives at a relatively low yield from multicomponent reaction of three components 2-(thiophen-2-yl)-1H-indole, N-methylaniline and desired aldehydes. The anticancer effect of the newly synthesized derivatives was determined against different cancers, colon, lung, breast and skin. The counter screening was done against normal Epithelial cells (RPE-1). The effect on cell cycle and mechanisms underlying of the antitumor effect were also studied. All new compounds were initially tested at a single dose of 100 μg/ml against this panel of 5 human tumor cell lines indicated that the compounds under investigation exhibit selective cytotoxicity against HCT-116 cell line and compounds (4g, 4a, 4c) showed potent anticancer activity against HCT-116 cell line with the inhibitory concentration IC50 values were, 7.1±0.07, 10.5± 0.07 and 11.9± 0.05 μΜ/ml respectively. Also, the active derivatives caused cell cycle arrest at the S and G2/M phase with significant(p < 0.0001) increase in the expression levels of tumor suppressors miR-30C, and miR-107 and a tremendous decrease in oncogenic miR-25, IL-6 and C-Myc levels. It is to conclude that the anticancer activity could be through direct interaction with tumor cell DNA like S-phase-dependent chemotherapy drugs. Which can interact with DNA or block DNA synthesis such as doxorubicin, cisplatin, or 5-fluorouracil and which were highly effective in killing the cancer cells. This data ensures the efficiency of the 3 analogues on inducing cell cycle arrest and preventing cancer cell growth. The altered expressions explained the molecular mechanisms through which the newly synthesized analogues exert their anticancer action. [ABSTRACT FROM AUTHOR]

This work explores the synthesis and DFT study of five tetranuclear Pb(II) complexes and the role of tetrel bonding in their crystal engineering. Three synthesised Pb(II) complexes and two theoretical tetrameric Pb(II) complexes with halogenated thiophene carboxylate and 1,10-phenanthroline ligands are reported here. Their structural configurations, which feature chair-like repeating units connected via oxygen bridges, without Pb–Pb bonds, show two types of packing arrangements. Each Pb atoms form hemidirectional coordination creating space for the formation of tetrel bonds. The close packed arrangements are stabilised and guided by tetrel bonds. The Pb⋯Br tetrel bonds were found to contribute −4.38 kcal mol−1 and Pb⋯Cl −3.37 kcal mol−1 for the stability of the complexes. These tetrel bonds direct the packing arrangements within the crystal lattice. Additionally, open packed arrangements are stabilised by hydrogen bonds. These findings offer new insights into the design of lead-based metal organic frameworks and highlights the critical role of tetrel bonds in the crystal architecture. [ABSTRACT FROM AUTHOR]

Compounds containing the thiophene moiety find several applications in physics and chemistry, such as electrical conduction, which depends on specific conformations to properly exhibiting the desired properties. In turn, chalcogen bonding has found to modulate the conformation of some N‐thiophen‐2‐ylfomamides. Since halogens participate in a kin interaction (halogen bonding) and are abundant in agrochemicals, pharmaceuticals, and materials, we have quantum‐chemically explored the interaction between organic halogen and thiophene as a conformational modulator in some model compounds. Although such interaction indeed appears, as demonstrated by atoms in molecules and natural bond orbital analysis, it is inefficient to control the conformational equilibrium. An energy decomposition analysis scheme demonstrated that halomethane and thiophene tend to move away from one another due to a core component (Pauli repulsion and exchange), which is mainly due to a deformation term. Therefore, chalcogen bonds with halogens appear weaker than with other chalcogens. [ABSTRACT FROM AUTHOR]

Doping of organic semiconductors has served as an effective method to achieve high electrical conductivity and large thermoelectric power factor. This is of importance to the development of flexible/wearable electronics and green energy‐harvesting technologies. The doping impact of the Lewis acid tris (pentafluorophenyl) borane (BCF) on the thermoelectric performance of poly(2‐(4,4′‐bis(2‐methoxyethoxy)‐5′‐methyl‐[2,2′‐bithiophen]‐5‐yl)‐5‐methylthieno[3,2‐b]thiophene (pgBTTT), a thiophene‐based polymer featuring oligoethylene glycol side chains is investigated. Tetrafluorotetracyanoquinodimethane (F4TCNQ), a well‐established dopant, is utilized as a comparison; however, its inability to co‐dissolve with pgBTTT in less polar solvents hinders the attainment of higher doping levels. Consequently, a comparative study is performed on the thermoelectric behavior of pgBTTT doped with BCF and F4TCNQ at a very low doping level. Subsequent investigation is carried out with BCF at higher doping levels. Remarkably, at 50 wt% BCF doping level, the highest power factor of 223 ± 4 µW m−1 K2 is achieved with an electrical conductivity of 2180 ± 360 S cm−1 and a Seebeck coefficient of 32 ± 1.3 µV K−1. This findings not only contribute valuable insights to the dopant interactions with oxygenated side chain polymers but also open up new avenues for high conductivity thermoelectric polymers in flexible electronic applications. [ABSTRACT FROM AUTHOR]

Dye‐containing polymers P1 (PEDPP‐OT‐BDT) and P2 (PEDPP‐OT‐BDTT) including a π‐extended diketopyropyrrole (DPP) derivative and electron‐rich thiophene fused ring units (4,8‐bis((2‐ethylhexyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene for P1 and 4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene for P2) were synthesized as narrow band gap dyes. A π‐extended DPP (EDPP‐OT‐BrPh), fragment of the polymers P1 and P2, was obtained by extending the π‐conjugation of DPP using Ru(III)‐catalyzed C−H and N−H activation reported by Gońka et al. in 2019, exhibiting a high quantum yield (ϕem=0.84) and small HOMO‐LUMO gap (Eg=1.69 eV) due to the spatial overlap of the HOMO and LUMO orbitals. The solubility of the π‐extended DPP was improved by introducing four 2‐octylthophene side chains around the periphery of the planer dye moiety, while maintaining the high planarity of the dye molecule, which is essential to the function of optoelectronic devices. As a result, P1 and P2, polymerized with the π‐extended DPP and BDT derivatives, exhibit carrier mobility of approximately 10−5 cm2/Vs in organic field‐effect transistors (OFETs). In bulk heterojunction (BHJ) solar cells with [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM), they demonstrate a power conversion efficiency (PCE) of 1.0 % with an average transmittance (AVTs) of around 60 %. [ABSTRACT FROM AUTHOR]

Unexpectedly facile dearomative intramolecular (4+3) cycloadditions of thiophenes with epoxy enolsilanes, providing sulfur‐bridged cycloadducts, are reported. A total of fifteen thiophene substrates have been found to undergo (4+3) cycloaddition smoothly to produce endo and exo (4+3) adducts in yields of up to 83 % with moderate to good diastereoselectivity. Complete conservation of enantiomeric purity was observed when the optically enriched epoxide was used. The desulfurizing transformations of the sulfur‐bridged skeleton of the cycloadducts provide functionalized 6,7‐fused bicyclic frameworks consisting of 1,3‐cycloheptadiene subunits. Density functional theory calculations reveal the origins of the facile dearomatization of thiophenes in these (4+3) cycloadditions. [ABSTRACT FROM AUTHOR]

The current bottleneck in the development of efficient photocatalysts for hydrogen evolution is the limited availability of high‐performance acceptor units. Over the past nine years, dibenzo[b,d]thiophene sulfone (DBS) has been the preferred choice for the acceptor unit. Despite extensive exploration of alternative structures as potential replacements for DBS, a superior substitute remains elusive. In this study, a symmetry‐breaking strategy was employed on DBS to develop a novel acceptor unit, BBTT‐1SO. The asymmetric structure of BBTT‐1SO proved beneficial for increasing multiple moment and polarizability. BBTT‐1SO‐containing polymers showed higher efficiencies for hydrogen evolution than their DBS‐containing counterparts by up to 166 %. PBBTT‐1SO exhibited an excellent hydrogen evolution rate (HER) of 222.03 mmol g−1 h−1 and an apparent quantum yield of 27.5 % at 500 nm. Transient spectroscopic studies indicated that the BBTT‐1SO‐based polymers facilitated electron polaron formation, which explains their superior HERs. PBBTT‐1SO also showed 14 % higher HER in natural seawater splitting than that in deionized water splitting. Molecular dynamics simulations highlighted the enhanced water‐PBBTT‐1SO polymer interactions in salt‐containing solutions. This study presents a pioneering example of a substitute acceptor unit for DBS in the construction of high‐performance photocatalysts for hydrogen evolution. [ABSTRACT FROM AUTHOR]

Two new dyes were obtained; their D—A—π—A′ structure included benzo[d][1,2,3]-thiadiazole as an internal acceptor (A), a cyanoacrylic acid residue as a terminal anchor acceptor (A′), a 4H-cyclopenta[2,1-b:3,4-b′]dithiophene π-spacer with branched alkyl groups, and 2,3-dihydroindole condensed with carbocycles as a donor. The optical and electrochemical characteristics of the obtained dyes were determined, and solar cells based on them were assembled. The power conversion efficiency reached 3.05% for a device based on the dye containing a 2,3,4,4a,9,9a-hexahydro-1H-carbazole donor moiety. The relatively low value of photovoltaic efficiency is likely due to excessive steric effects that are demonstrated by the branched alkyl groups when the dyes are sorbed onto the TiO2 surface, which leads to an insufficient concentration of the dye on the electrode surface, resulting in a decrease in the quantity of absorbed photons. [ABSTRACT FROM AUTHOR]

Photoresponsive conjugated polymers are a promising target for modern organic electronics. Numerous photoswitchable repeat units have been included covalently within polymeric structures to enable responsive chromic materials, most commonly through side‐chain appendages or through formal conjugation along a π‐conjugated backbone. We recently disclosed a new design whereby the photoswitch elements are cross conjugated to a conjugated polymer main chain. In this case, we found that the extent of photoconversion was dictated in part by competitive main chain light absorption, which could be suppressed by using a photoswitching motif that carried most of the frontier molecular orbital densities. Here, we report the modeling and synthesis of a series of thieno[3,4‐b]thiophene (TT)‐based photochromes with various aromatic flankers imparting varying degrees of steric bulk and π‐conjugation in order to elucidate the balancing act between steric and electronic factors to promote photochromism. These model systems provide a better understanding of the behavior of photochromic units within extended oligomeric and polymeric π‐conjugated materials. [ABSTRACT FROM AUTHOR]

The present work details the synthesis of several intriguing nitrogenous heterocycles utilizing a cyano-N-aryl-acetamide-reagent, notably chlorinated thiazolidine, thiophene and 2-iminochromene derivatives. Thus, the precursor 2-cyano-N-(2,4-dichlorophenyl) acetamide 1 underwent the reaction with phenyl isothiocyanate in DMF/KOH to afford the intermediate salt 3, which reacted in situ with several α-halogenated reagents 4a-c like ethylchloroacetate,α-bromoethylpropionate and α-bromo ethyl butaneoate and afforded the corresponding 4-thiazolidinnone derivatives (6a–c, yield%; 67–85), thiophene derivatives (11;yield 80%) and (15, yield 77%) obtained from the reaction of 3 with α- chloroacetyl acetone 9 and ethyl 2-chloro-3-oxobutanoate 12.Novel series of different 4-thiazolidinones(16a–e; yield%; 65–84) were obtained via condensation of 6a with different aldehydes. Finally, the reaction of compound 1 with different bifunctional reagents, such as salicylaldehyde derivatives and 2-hydroxynaphthaldehyde, in ethanol furnished the iminochromenes (17a,b; yield %77,80) and (18; yield 85%). In addition, molecular docking studies of the prepared molecules were carried out against papain-like protease (PLpro) to identify novel promising inhibitors of Coronavirus Disease COVID-19. The binding affinity of the best docked compounds 16c and 16a toward the target enzyme was − 9.6 and − 8.9 kcal/mole, respectively. In silico-docking-Studies indicate, that compounds 16c and 16a have the potential as antiviral against COVID-19. [ABSTRACT FROM AUTHOR]

Two solvent-controlled Cd(II) compounds, formulated as {[Cd2(Htdc)4(µ-imyp)(H2O)4]} (1), [Cd2(µ2-tdc)2(µ-imyp)(DMF)2(H2O)2]n (2) (H2tdc= 2,5-thiophenedicarboxylic acid, imyp = 4-imidazol-1-yl-pyridine and DMF = N,N-dimethylformamide) have been synthesized by reactions of Cd(NO3)2·4H2O and H2tdc with imyp in different solvents, respectively. Both compounds were then characterized by single-crystal X-ray diffraction and other physicochemical methods. In 1, partially deprotonated Htdc− anion as terminal ligand and µ-imyp ligand connect Cd2+ ions to generate a discrete structure. In 2, completely deprotonated µ2 – tdc2− anions and µ-imyp ligand link Cd2+ ions into a 1D double chain structure. Both compounds display 3D supramolecular structures through hydrogen bonding interactions. The results provided interesting insights into solvent effects on the structural formation of compounds 1 and 2. In addition, the solid-state photoluminescent properties of compounds 1 and 2 were also investigated. Two solvent-controlled Cd(II) compounds have been synthesized by reactions of Cd(NO3)2·4H2O and 2,5-thiophenedicarboxylic acid with 4-imidazol-1-yl-pyridine in the different solvents. One compound is a discrete structure, while the other compound has a 1D double chain structure. The results provided interesting insights into solvent effects on the structural formation of compounds. [ABSTRACT FROM AUTHOR]

In this study, we focused on the synthesis and molecular docking investigations of hybrid derivatives containing tetrahydrobenzo[b]thiophene. Our aim was to evaluate their potential antibacterial properties. Through our analysis, we aimed to gain insights into the molecular mechanisms that underlie their effectiveness against bacterial infections. A series of tetrahydrobenzo[b]thiophene derivatives were produced through the reaction of various carbonyl groups, including 2-thiophenaldehyde, 2-naphthaldehyde, and 3-acetylindole with (2-amino-N-(4-methoxyphenyl)-4-oxo-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxamide). Additionally, the condensing starting material with benzaldehyde, a new derivative linked to substituted pyrimidines was synthesized and named tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidine-4,5-dione. Furthermore, it underwent a reaction with monochloroacetyl chloride to produce another derivative. The production and synthesis processes all involved the use of tetrahydrobenzo[b]thiophene compounds. [ABSTRACT FROM AUTHOR]

The unique characteristics of an anti‐ambipolar switch (AAS) device exhibit Λ‐shaped transfer responses (namely delta conductance) and present unique opportunities to overcome the limit of silicon‐based, complementary metal‐oxide‐semiconductor (CMOS) logic circuits. It is crucial because a device that only turns on under a certain bias range can be utilized to simplify the logic circuit and reduce the device count and circuit area required to perform logic functions. In this study, a physically scalable AAS device is investigated using ZnO and dinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene as heterojunction structures to reduce the operating voltage and enhance the peak current and peak‐to‐valley ratio of the AAS device. Moreover, novel logic circuits for AND, OR, XOR, DEMUX, and half‐adder functions are demonstrated using AAS devices. AAS device‐based logic circuits exhibit power‐efficiency characteristics (≈49 times lower than that of the 90‐nm silicon‐based CMOS inverter) and reduce the transistor count and the circuit area by ≈67% and ≈70%, respectively. These results indicate that the use of AAS device‐based logic circuits can be a promising approach to overcome the physical scaling limit of current CMOS technology. [ABSTRACT FROM AUTHOR]

Thiophenes and 1,2,3‐NH‐triazoles are important frameworks in pharmaceuticals and advanced functional materials. Vinyl sulfones are also blueprint motifs in medicinal chemistry, but hybrid analogues of 1,2,3‐NH‐triazole‐derived from vinyl sulfones still need to be explored. In this report, we present an efficient and transition‐metal‐free [4+1]‐thioannulation of sulfonyl‐tethered 1,3‐enynes with Na2S in the presence of Cs2CO3 to generate 2,4‐disubstituted thiophenes in good to high yields. We also established a formal [3+2]‐cycloaddition of 1,3‐sulfonylenynes with NaN3 under metal‐ and base‐free conditions to synthesize vinyl sulfone‐containing 1,2,3‐NH‐triazole derivatives in moderate to high yields. The scope of these protocols was successfully showcased with various types of 1,3‐enynes bearing sensitive functional groups and complex structural scaffolds. The desired products were readily obtained with good functional group tolerance and compatibility. Based on the existing results and control experiments, plausible mechanistic pathways are also presented. [ABSTRACT FROM AUTHOR]

Three examples of meso‐triaryl trithiapentaphyrin(2.2.1.1.1)s 1–3 (Figure 1) that contains three thiophenes and two pyrrole rings connected via seven meso‐carbons were synthesized by condensing newly synthesized benzo‐fused trithiatripyrrane diol and appropriate meso‐aryl dipyrromethane under mild acid catalysed conditions in 5–8 % yields. In these macrocycles, two of the meso‐positions were fused with the benzene rings and the DFT optimized structural analysis revealed that the macrocycles adopt saddled conformation with the two thiophene rings oriented towards outside the macrocyclic core. HR‐MS and detailed 1D & 2D NMR studies were used in deducing the molecular structures of the macrocycles and NMR studies support their nonaromatic nature. The macrocycles exhibit one strong sharp absorption band at ~430 nm and a broad band in the region of 550–850 nm which were further red‐shifted to NIR region in their protonated derivatives. The macrocycles exhibit two reversible oxidations and one reduction and the redox data revealed that the macrocycles were easier to oxidize and were electron‐rich. [ABSTRACT FROM AUTHOR]