Delocalization Research Articles

Endothermic Charge Separation Occurs Spontaneously in Non-Fullerene Acceptor/Polymer Bulk Heterojunction.

Organic photovoltaics (OPVs) based on non-fullerene acceptors (NFAs) have achieved a power conversion efficiency close to 20%. These NFA OPVs can generate free carriers efficiently despite a very small energy level offset at the donor/acceptor (D/A) interface. Why these NFAs can enable efficient charge separation (CS) with low energy losses remains an open question. Here, the CS process in the PM6:Y6 bulk heterojunction (BHJ) is probed by time-resolved two-photon photoemission (TR-TPPE) spectroscopy. We found that the CS, the conversion from bound charge transfer (CT) excitons to free carriers, is an endothermic process with an enthalpy barrier of 0.15eV. The CS can occur spontaneously despite being an endothermic process, which implies that it is driven by entropy. We further argue that the morphology of the PM6:Y6 film and the anisotropic electron delocalization restrict the electron and hole wavefunctions within the CT exciton such that they can primarily contact each other through point-like junctions. This configuration can maximize the entropic driving force. This article is protected by copyright. All rights reserved.

Tuning Electron Delocalization of Redox-Active Porous Aromatic Framework for Low-Temperature Aqueous Zn-K Hybrid Batteries with Air Self-Chargeability.

Air self-charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self-charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low-temperature self-charging aqueous Zn-K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)-based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn-ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all-climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self-charging process in the absence of an external power source. Impressively, the air self-charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g-1), and exceptional self-charging performance even at -40 °C. Therefore, the development of self-charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Tuning Electron Delocalization of Redox‐Active Porous Aromatic Framework for Low‐Temperature Aqueous Zn−K Hybrid Batteries with Air Self‐Chargeability

AbstractAir self‐charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self‐charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low‐temperature self‐charging aqueous Zn−K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)‐based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn‐ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all‐climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self‐charging process in the absence of an external power source. Impressively, the air self‐charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g−1), and exceptional self‐charging performance even at −40 °C. Therefore, the development of self‐charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Electronic Delocalization Engineering of β‐AsP Enabled High‐Efficient Multisource Logic Nanodevices

AbstractDelocalized electron and phonon structures are directives for rationally tuning the intrinsic physicochemical properties of 2D materials by redistributing electronic density. However, it is still challenging to accurately manipulate the delocalized electron and systematically study the relationships between physiochemical properties and practical nanodevices. Herein, the effects of delocalized electrons engineering on blue‐arsenic‐phosphorus (β‐AsP)‐based practical devices are systematically investigated via implementing vacancies or heteroatom doping. A tendency of carrier conductivity property from “half‐metal” to “metal” is initially found when tuning the electronic structure of β‐AsP with adjustable vacancy concentrations below 2 at% or above 3 at%, which can be ascribed to the introduction of delocalized electrons that cause asymmetric contributions to the electronic states near the implementation site. In optical logic device simulations, broadband response, triangular wave circuit system signal, and reverse polarization anisotropy are achieved by adjusting the vacancy concentration, while extinction ratios are as high as 1561. The electric and thermic‐logic devices realize the highest available reported giant magnetoresistance (MR) up to 1013% and 1039% at vacancy concentrations of 1.67% and 0.89%, respectively, which is significantly superior to the reports. The results shed light on the electronic delocalization strategy of regulating internal structures to achieve highly efficient nanodevices.

THEORETICAL PREDICTION AND COMPREHENSIVE CHARACTERIZATION OF AN ALL-NITROGENATOMIC RING, CYCLO[18]NITROGEN (N18).

The cyclic molecule cyclo[18]carbon composed of 18 carbon atoms has been observed in condensed phase experiment in recent years and has attracted great attention. Through state-of-art quantum chemistry calculation, this study found that 18 nitrogen atoms can also form a macrocyclic system, cyclo[18]nitrogen (N18), though its lifetime is very short at room temperature and can only exist for a relatively long time at very low temperatures. We comprehensively theoretically studied properties of N18, including geometric configurations, thermal decomposition mechanism and rate, molecular dynamics behavior, energetic properties, vibrational and electronic spectra. We also discussed in depth the electronic structure of N18, including nature of the N-N bonds, lone-pairs, charge distribution characteristics, electronic delocalization, and aromaticity. This work is not only the first exploration of the macrocyclic N18 molecule, but also the first time to systematically examine a very long-chain substance fully composed of nitrogen atoms in isolated state.

Switching CO2 Electroreduction toward Ethanol by Delocalization State-Tuned Bond Cleavage.

The electrochemical CO2 reduction reaction by copper-based catalysts features a promising approach to generate value-added multicarbon (C2+) products. However, due to the unfavored formation of oxygenate intermediates on the catalyst surface, the selectivity of C2+ alcohols like ethanol remains unsatisfactory compared to that of ethylene. The bifurcation point (i.e., the CH2═CHO* intermediate adsorbed on Cu via a Cu-O-C linkage) is critical to the C2+ product selectivity, whereas the subsequent cleavage of the Cu-O or the O-C bond determines the ethanol or ethylene pathway. Inspired by the hard-soft acid-base theory, in this work, we demonstrate an electron delocalization tuning strategy of the Cu catalyst by a nitrene surface functionalization approach, which allows weakening and cleaving of the Cu-O bond of the adsorbed CH2═CHO*, as well as accelerating hydrogenation of the C═C bond along the ethanol pathway. As a result, the nitrene-functionalized Cu catalyst exhibited a much-enhanced ethanol Faradaic efficiency of 45% with a peak partial current density of 406 mA·cm-2, substantially exceeding that of unmodified Cu or amide-functionalized Cu. When assembled in a membrane electrode assembly electrolyzer, the catalyst presented a stable CO2-to-ethanol conversion for >300 h at an industrial current density of 400 mA·cm-2.

The key role of methylenediammonium and tetrahydrotriazinium in the phase stability of FAPbI3

Formamidinium lead triiodide (FAPbI3) is the prime candidate for single-junction perovskite solar cells, despite the metastability of the phase. To improve its ambient-phase stability and produce world-record photoelectric conversion efficiencies, methylenediammonium (MDA) has been used as an additive in FAPbI3. However, the exact function and role of MDA are still uncertain. The MDA doping may exist in the perovskite lattice in either the original structure or the THTZ-H (tetrahydrotriazinium) structure. In this research, the effects of the MDA and THTZ-H doping FAPbI3 perovskite on its stability are explored by first-principles calculations. Both MDA and THTZ-H doping can improve the stability of FAPbI3 perovskite from a structural perspective due to lattice strain and stronger H–I bonds. However, the doping mechanisms differ significantly in terms of electronic properties. The MDA doping acts by the traditional passivation mechanism. It can eliminate the iodine interstitial defect states that trap charge carriers and inhibit iodine interstitial defect migration. The THTZ-H cation can directly contribute to the band edge construction in the FAPbI3 bulk. Electron delocalization in the π-conjugated ring structure lowered the frontier orbital separation of the THTZ-H organic molecule and enabled orbital overlap with the inorganic moiety. The in-depth understanding of the mechanism of improving stability in this study would facilitate the application of FAPbI3 perovskite optoelectronic devices.

Structural evolution and electronic properties of medium-sized boron clusters doped with selenium

The exploration of boron-doped clusters' structures and properties significantly advances our understanding of nanomaterials at the microscopic level. This study employs density functional theory to systematically investigate the structural evolution and electronic properties of singly Se-doped boron-based clusters, SeBn− (n = 16–24). The dopant atom exhibits a distinct preference for positioning outside the Bn−/0 framework, mirroring the arrangement found in the corresponding pure boron skeleton. Predicting the structural and electronic properties of doped clusters using simulated photoelectron spectra. Notably, magic clusters SeB19− and SeB23− are identified, showcasing remarkable relative stability. Furthermore, SeB24− is suggested to potentially exist as a pseudo-tubular isomer, representing a unique three-dimensional structure. The natural population analysis uncovers an electron transfer from Se to B atoms. The electronic localization function highlights substantial electron delocalization in SeBn−. Additionally, isochemical shielding surface analysis reveals pronounced aromaticity in the pseudo-tubular SeB24− isomer, thereby significantly enhancing the overall stability of the clusters.

Defect Engineering for Enhanced Electrocatalytic Oxygen Reaction on Transition Metal Oxides: The Role of Metal Defects.

Metal defect engineering is a highly effective strategy for addressing the prevalent high overpotential issues associated with transition metal oxides functioning as dual-function commercial oxygen reduction reaction/oxygen evolution reaction catalysts for increasing their activity and stability. However, the high formation energy of metal defects poses a challenge to the development of strategies to precisely control the selectivity during metal defect formation. Here, density functional theory calculations are used to demonstrate that altering the pathway of metal defect formation releases metal atoms as metal chlorides, which effectively reduces the formation energy of defects. The metal defects on the monometallic metal oxide surface (Mn, Fe, Co, and Ni) are selectively produced using chlorine plasma. The characterization and density functional theory calculations reveal that catalytic activity is enhanced owing to electronic delocalization induced by metal defects, which reduces the theoretical overpotential. Notably, ab initio molecular dynamics calculations, ex situ XPS, and in situ ATR-SEIRAS suggest that metal defects effectively improve the adsorption of reactive species on active sites and enhance the efficiency of product desorption, thereby boosting catalytic performance.

Utilizing a Carbazole‐Incorporated Regioisomeric Synthesis Strategy to Design Hole Transporting Materials for Perovskite Solar Cells

Two new p‐type molecules, namely TAT‐TY3 and TAT‐TY4, featuring triazatruxene endcaps and carbazole π‐bridges, were synthesized. The photophysical and electrochemical properties of synthesized materials were comparatively investigated based on their 2,7‐ and 3,6‐carbazole conjugation pathways. Optical characterizations revealed the impact of non‐bonding electron delocalization of triazatruxene through carbazole moieties, resulting in a significant increase in absorption intensity corresponding to n‐π* energy transitions and a red shift of triazatruxene moieties. Consequently, the optical band gaps of TAT‐TY3 and TAT‐TY4 were measured at 3.0 and 3.2 eV, respectively. Moreover, the molecules' first oxidation potentials exhibited a drastic difference due to the electrochemical behavior of 2,7‐ and 3,6‐carbazole moieties. The highest occupied molecular orbital (HOMO) level for TAT‐TY3 was measured to be ‐5.02 eV, while for TAT‐TY4, it was measured as ‐4.67 eV. Hole‐extraction properties were explored using steady‐state and time‐resolved photoluminescence spectroscopy, revealing enhanced charge transfer between the TAT‐TY3/Perovskite interface due to the better alignment of HOMO energy levels. The photovoltaic performances of the hole‐transporting materials (HTMs) were successfully characterized in triple‐cation perovskite solar cells and efficiencies of up to 17.9%, 16.2%, and 9.8% were achieved for Spiro‐OMeTAD, TAT‐TY3, and TAT‐TY4, respectively.

Evaluation of the binding efficacy of flavonol derivatives on estrogen receptors (ER) with respect to ring B hydroxylation

RationaleFlavonols are a class offlavonoidsthat have a 3-hydroxyflavonebackbone with an additional ketone group. Galangin is a form of flavonols formed with additional hydroxy groups at ring A positions 5 and 7. The hydroxylation at ring B of galangin may result in resonance and delocalization of electrons and the formation of different derivatives like kaempferol, quercetin, and myricetin. Most of these flavonols have a similarity to 17β-estradiol, the steroid sex hormone which bound to estrogen receptors (ER), a class of nuclear transcription factors involved in the regulation of many complex pathophysiological processes including breast cancer genesis and progression. Various studies have reported that most of the flavonols are antiestrogenic and show anticancer potential, but the mechanisms may be varied like estrogenic, anti-estrogenic, non-estrogenic, and biphasic activities and their mechanisms of action have not been systematically evaluated. AimThe goal of this study is to ascertain the possible interactions of flavonol derivatives to ER with respect to ring B hydroxylation and the unsaturation degree of the C2′=C3′ bond. MethodsThe variations in structure, frontier molecular orbital, molecular electrostatic potential maps, Mullikan charge population of derivatives was determined by Density functional theory (DFT) calculations at B3LYP/6-311G (d,p) level on model molecular systems. A deep insight into these interactions with ER was described by molecular docking studies. Results and discussionResults shows that the flavonol was found more affinity to ERβ and the efficacy was increased with respect to the OH group on ring B. The hydroxyl group at position 3 and 5 in ring A and C are not found much relevant. The site of ERβ is more hydrophilic while binding ligand and the electropositive and electronegative area of the molecule was increased and reaches a maximum for quercitin with the 3 OH group; after that, it found to diminish. Moreover, the reduced cavity size of ERβ and the replacement of LEU 384 with polar HIE 475 and MET 336 increased the polarity and hydrophilicity of the cavity and led to more electrostatic interaction with ligands. ERα is found to be hydrophobic and the polar interaction between the ligands and ERa is less due to open confirmation of the cavity and bulk empty space. The results also emphasize that myricetin and quercetin require less energy to activate while accounting for the values of Gibbs free energy, the electronic configuration of frontier molecular orbitals, and entropy. ConclusionThe hydroxylation on ring B has a significant importance in the chemical reactivity as well as estrogenic activity of flavonol.

Boosting persulfate activation through efficient π → π* transition activated by Cu ion anchored porphyrin-based metal–organic framework

Photocatalytic persulfate activation provides a promising approach for the elimination of persistent organic pollutants from water. This has been exemplified in porphyrin-based metal organic frameworks (PMOFs), which however come with ineffective electron transition within the porphyrin ligand. Herein, we present a Cu ion modification strategy capable of boosting electron transition by inducing electron delocalization under visible light. The introduction of Cu ions increased the degradation rate constant of ciprofloxacin (CIP) by nearly 44 times, surpassing most state-of-the-art photocatalysts. The in-situ characterizations and theoretical calculations suggest that π-electron localization constitutes the origin of ineffective electron transition in PMOFs. The introduction of Cu ions induces π-electron delocalization to intensify the π → π* transition, forming electron-rich centers of Cu to lower the energy barrier for O-O bond cleavage. This work offers fundamental insights into the electron transition within PMOFs, upon which the universal strategy is proposed for improved water decontamination performance via persulfate activation.

Regulating intramolecular hydrogen bonds of p-phenylenediimidazole- based small-molecule compounds towards the enhanced lithium storage capacity

The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance, abysmal conductivity, and the resultant low practical capacity. To address these issues, a class of bipolar p-phenylenediimidazole-based small-molecule compounds are designed and fabricated. The π-conjugated backbone of these small molecules allows for electron delocalization on a big conjugation plane, endowing them with good conductivity and reaction reversibility. Furthermore, when the para-positions of phenylene are occupied by hydroxyl groups, as-formed intramolecular hydrogen bonds (N-H…O) between phenolic hydroxyl groups and the -NH groups of imidazole rings further enhance the structural planarity, resulting in higher π-conjugation degree and better conductivity, and thus higher utilization of active sites and electrode capacity, proved by both experimental results and theoretical calculations. The optimized composite electrode DBNQ@rGO-45 shows a high specific capacity (∼308 mA h g−1 at 100 mA g−1) and a long cycling stability (112.9 mA h g−1 after 6000 cycles at 2000 mA g−1). The significantly better electrochemical properties for hydroxyl group-containing compounds than those without hydroxyl groups attributed to intramolecular hydrogen bond-induced conjugation enhancement will inspire the structure design of organic electrodes for better energy storage.

Activated Carbon Anchoring Site Enrichment Through B and N Codoping for Boosting Bi2Mo2.5(S,O)10 Oxysulfide Catalyst Stability and Visible‐Light‐Driven Hydrogen Evolution

AbstractBoron and nitrogen can enter the carbon lattice and provide structural disorder, porous structure, and active sites for better catalyst dispersions and activity. Herein, Bi2Mo2.5(S,O)10 oxysulfide (BiMoOS) anchored on unmodified and surface‐modified activated carbon (AC) via B and N doping is synthesized for efficient PHER, aiming that B and N doping into carbon framework can modify the surface textural features which act as anchoring sites for the host Bi2Mo2.5(S,O)10 and boost its photocatalytic activity by increasing specific surface area via preventing aggregation through a uniform distribution. Thus, the BiMoOS@B─N─AC catalyst achieved excellent stability and PHER performance (564.2 µmol h−1 H2 under visible light). The doped B and N in AC create structural disorder/defects, active sites and induce electron delocalization in B─N─AC, used as the anchoring sites for BiMoOS catalysts and stimulate the adsorption and activation kinetics of the H2O molecules, and also provide a highly conductive network that enhances charge transport and stability of BiMoOS@B─N─AC. With the advantages of the modified B─N─AC, the oxygen vacancy‐anchored BiMoOS exhibited superb PHER. Hence, B and N co‐doping into the carbon lattice is a promising approach to enriching the anchoring site for boosting metallic nanocatalyst stability and catalytic performance.

A novel chain-like conjugated donor-π-acceptor molecular additive for highly efficient and stable perovskite solar cells

In donor-π-acceptor (D-π-A) molecules, the coordination ability of the acceptor can be enhanced by the directed movement of delocalized electrons (DEs) on the π-bridge. However, the conventional aromatic ring as π-bridge limits the number of DEs due to the structural characteristic, which restrict the coordination ability of the acceptor, and there is still a lack of research on this issue. Herein, we proposed a chain-like conjugated π-bridge design strategy to address this issue. The Astaxanthin with eleven contiguous C − C = C fragments was selected as a chain-like D-π-A additive for perovskite films. Twenty-two DEs in such chain-like bridge can move towards the C = O group by the D-π-A effect within Astaxanthin, which increases the electron cloud density of C = O group so that enhances its coordination capacity with cations. Ultimately, the Astaxanthin-based device achieved a champion power conversion efficiency (PCE) of 24.43 % and maintained more than 95 % and 91 % of initial PCE for aging 1000 h in dry air (RH < 1 %) and atmosphere (RH = 20 ∼ 30 %), respectively. This work provides a novel strategy to break the restriction of aromatic rings to DEs, which provides theoretical and experimental guidance for further designing chain-like D-π-A additives with strong defect passivation ability to boost photovoltaic performance of PSCs.

Density functional theory study on interatomic forces and electronic properties of ConMoP(n = 1 ~ 5) cluster

AbstractTo delve into the microscopic property variations of the ConMoP(n = 1 ~ 5) cluster, this study employs density functional theory at the B3LYP/def2‐TZVP quantum chemistry level. The paper conducts a comprehensive theoretical analysis of the clusters, examining parameters such as bond lengths, bond angles, electronic localization function (ELF), interaction region indicator function (IRI), independent gradient model based on the Hirshfeld partition, deformation density, electronic space range, chemical hardness and softness, polarizability, and dipole moment. The optimization process reveals 16 stable configurations for the ConMoP(n = 1 ~ 5) cluster, predominantly taking on a steric form. As the cluster size increases, the electronic delocalization of Co atoms intensifies, while the electronic properties of Mo atoms remain relatively stable. Notably, P atoms maintain a high degree of electronic delocalization. The interatomic forces within the clusters predominantly exhibit covalent bonding, with no evident repulsive effects observed between atoms. The bonding between metal atoms in the clusters leans toward a preference for covalent interaction. The degree of dispersion in the clusters increases with their growth, particularly evident in configuration 5‐a, which displays a broader spatial distribution. Configuration 3‐a demonstrates the most favorable activity, showcasing a relatively stable structure. Overall, configuration 3‐a emerges as a focal point for catalytic reactions. This article provides a more comprehensive analysis of the ConMoP(n = 1 ~ 5) cluster, yielding diverse results and enhancing the theoretical understanding of this cluster.

Dual ligands and crosslinking atoms relayed MOF anode for tetracycline hydrochloride electrocatalytic decontamination: Efficiency and mechanism

MOF anodes were especially prepared with dual-ligand and S/N crosslinking atoms for tetracycline hydrochloride (TCH) electrocatalytic degradation. Results showed S(HTTP)-Ni-N(HAB) and N(HITP)-Ni-S(BHT) exhibited high electrocatalytic performance with 100% TCH degradation in 10 min, which were superior to that of S(HTTP)-Ni-S(BHT) and N(HITP)-Ni-N(HAB). The experimental and DFT calculation results jointly unraveled that the electron delocalization created by adjacent S/N crosslinking atoms facilitated the electron conduction and produced positive-charged Ni sites for the improved generation of ·O2− and ·OH radicals. The positive contributions of ·O2− and ·OH radicals then proved the degradation pathways of TCH. In addition, extended experiments on various conditions and pollutions highlighted the application potential of S/N hybrid MOF anodes. The final results provided new insight into MOF anode design and preparation via large cardinal ligand and crosslinking atom adjustment for environmental application.

Electronic Delocalization and σ-Aromaticity in Heterometallic Cluster with Multiple Thorium-Palladium Bonds.

Research on metal-metal bonds involving f-block actinides, such as thorium, lags far behind the well-studied metal-metal bonds of d-block transition metals. The complexes with Th-TM bonds are extremely rare; all previously identified examples have only a single Th-TM bond with the Th center at an invariably +IV oxidation state. Herein, we report a series of Th2Pdn (n = 2, 3, and 6) clusters (complexes 3, 4, and 7) with multiple Th(III)-Pd bonds. Theoretical studies reveal that the Th2Pdn unit allows electronic delocalization and σ aromaticity, leading to unexpected closed-shell singlet structures for these Th(III) species. This electronic delocalization is evident in the highest occupied molecular orbital of Th(III) complexes and facilitates a 2e reduction of alkyne by complex 7, resulting in the formation of 8. Complexes 7 and 8 are distinctive in featuring a Th2Pd6 core with six and eight Th-Pd bonds, respectively, making them the largest known d-f heterometallic clusters exhibiting metal-metal bonding.

Design of dual-ligand coordination in metal organic frameworks for breaking the seesaw effect between de-NOx activity and N2 selectivity

In the selective catalytic reduction (SCR) of NOx with NH3, a catalyst usually exhibits a seesaw effect on de-NOx activity and N2 selectivity at low temperatures. Herein, we designed metal-organic frameworks (MOFs) with dual-ligand coordination to regulate the electronic and morphological structure for a breakthrough of the seesaw effect. The developed catalyst attained a noteworthy NOx conversion exceeding 90% within 60–330 ℃ with increased N2 selectivity. The dual-ligand coordination leads to more defects and a more uniform electron distribution for delocalization of electrons, thereby improving de-NOx activity. Furthermore, the dual-ligand coordination manifests a Si-O-Mn bond for amplifying both de-NOx activity and thermal stability. Additionally, the dual ligands and Mn produce a hollow sea-urchin-like morphology with more exposed active sites for concentrating reactants and intermediates to improve electron transfer efficiency in N2 selectivity. This work clarifies the mechanism of dual-ligand regulation for electron-morphology to simultaneously enhance de-NOx activity and N2 selectivity.

Effects of Connectivity Isomerization on Electron Transport Through Thiophene Heterocyclic Molecular Junction.

Connectivity isomerization of the same aromatic molecular core with different substitution positions profoundly affects electron transport pathways and single-molecule conductance. Herein, we designed and synthesized all connectivity isomers of a thiophene (TP) aromatic ring substituted by two dihydrobenzo[b]thiophene (BT) groups with ethynyl spacers (m,n-TP-BT, (m,n = 2,3; 2,4; 2,5; 3,4)), to systematically probe how connectivity contributes to single-molecule conductance. Single-molecule conductance measurements using a scanning tunneling microscopy break junction (STM-BJ) technique show ∼12-fold change in conductance values, which follow an order of 10-4.83 G0 (2,4-TP-BT) < 10-4.78 G0 (3,4-TP-BT) < 10-4.06 G0 (2,3-TP-BT) < 10-3.75 G0 (2,5-TP-BT). Electronic structure analysis and theoretical simulations show that the connectivity isomerization significantly changes electron delocalization and HOMO-LUMO energy gaps. Moreover, the connectivity-dependent molecular structures lead to different quantum interference (QI) effects in electron transport, e.g., a strong destructive QI near E = EF leads the smallest conductance value for 2,4-TP-BT. This work proves a clear relationship between the connectivity isomerization and single-molecule conductance of thiophene heterocyclic molecular junctions for the future design of molecular devices.