Electron Donor Research Articles

Visible light induced reactions of quinones

AbstractThis review covers the visible light induced reactions of quinones such as benzoquinone, naphthoquinone, and anthraquinone. These quinones are distinguished by their fully conjugated structures, which feature minimal energy gaps, and nonbonding electron pairs on the oxygen atoms. Such structural attributes facilitate np → π* transition, allowing for easy access to excited states and rendering quinones highly reactive under visible‐light irradiation. We describe three primary types of reactions facilitated by these electronic characteristics: Paternò–Büchi (PB) reactions, which entail [2 + 2] photocycloaddition between the carbonyl groups of quinones and alkenes or alkynes; CH activation processes, which showcase quinones' versatility in functionalizing hydrocarbons; and the formation of electron donor–acceptor complexes, demonstrating quinones' capability to engage in charge transfer interactions. Through this review, we highlight the critical role quinones play in photochemistry, their unique electronic properties, and their broad applicability in synthetic organic chemistry.

Visible-light-induced hydrosulfonylation of alkynes driven by electron-donor–acceptor (EDA) complexes

The method toward the vinyl sulfones has been realized by visible-light-induced hydrosulfonylation of alkynes via an EDA process. DIPEA was used as both electron donor for EDA complex and hydrogen donor for hydrogen atom transfer.

Recent Progress on Organic Electron Donors (OEDs) Enabled Radical Reactions

AbstractOver the past few decades, organic transformations facilitated by small organic molecules have witnessed considerable advancements. Small organic molecules have been widely applied to the construction of various skeletons. However, reduction as one of the fundamental reactions is generally initiated by metal‐containing reducing agents, although the initial progress of organic electron donors (OEDs) enabled reductive cleavage of some chemical bonds had been achieved in 1990s. Due to their structural diversity and tunability, OEDs can overcome the limitations of metal‐based reducing agents, such as low selectivity and poor functional group tolerance as well as the environmental problems caused by substantial inorganic waste after reactions. Building on a brief historical overview of OED research, this review focuses on the rencent advancements of the OEDs promoted radical reactions. It covers the reduction of C−X (X=C, O, N etc.) single bonds, radical cyclization, intermolecular radical addition to unsaturated bonds, radical coupling, functionalization of aromatics, and C−H bond activation. Additionally, the mechanistic insights of the typical reactions are highlighted for well understanding of the reaction mode involving OEDs.

Interfacial Assembly of Peptide Carbon Dot Hybrids Enables Photoinduced Electron Transfer with Improved Photoresponse.

Assemblies at the interface represent a powerful tool for integrating organic and inorganic components into hybrid nanostructures. Carbon dots are both excellent electron donors and acceptors, offering opportunities for their potential uses in light-harvesting applications. To further improve their functions, integration of acceptor carbon dots into donor organic nanostructures is of great interest for improving photophysical properties useful for photoinduced electron transfer. Here, a one-step protocol for the interfacial assembly of a two-component hybrid consisting of carbon dots and perylene containing an l-phenylalanine-based dipeptide through noncovalent bonding is developed. The perylene-containing dipeptide derivative formed micrometer-long nanofibers on the water surface through J-aggregate formation. Spectroscopic studies reveal photoluminescence quenching of the donor dipeptide upon increasing the concentration of acceptor carbon dots in the hybrid, suggesting photoinduced electron transfer from the donor peptides to acceptor carbon dots. The hybrids integrated in a planar device architecture show a significantly improved photoresponse because of the favorable interactions between the donor-acceptor components. The one-step integration of donor-acceptor hybrids on the water surface offers opportunities for light harvesting and related applications.

Isoreticular Squaraine-Linked Titanium-Organic Frameworks for Photocatalytic Water Splitting to Hydrogen Under Visible Light.

Inspired by the excellent photocatalytic activity of TiO2, titanium metal-organic frameworks (Ti-MOFs) with broad absorption of visible light are regarded as promising photocatalysts, but carboxylate-linkers used in them are mainly limited to the large extended π-electron systems. Developing Ti-MOFs using organic linkers with a donor-acceptor-donor (D-A-D) structure is expected to improve their charge separation but is still challenging. Herein the design of two new isoreticular Ti-MOFs, Ti6-SQ1 and Ti6-SQ2 are reported, by using squaraines bearing different electron donors as organic linkers. Discrete fourier transform (DFT) calculations demonstrate that ligand-to-metal charge transfer (LMCT) from the acceptor units of squaraines to the Ti6-oxo secondary building units (SBUs) drives the photocatalytic water splitting to hydrogen reaction. Compared with Ti6-SQ2, the shorter distance between the squaraine centers and the Ti6-oxo SBUs in Ti6-SQ1 makes stronger LMCT, showing higher photocatalytic hydrogen evolution efficiency of 11.5mmol g-1h-1 under visible light (λ > 420nm), which is ≈8 times that of Ti-based MOF photocatalysts reported so far. This work provides a new strategy to design Ti-MOF photocatalysts and understand their structure-property relationship.

Strategies for enhancing short- and medium-chain fatty acids synthesis from corn stover-based sugar: A new perspective on co-culture

In this study, corn stover-based sugar served as the initial carbon source to investigate the impact of different co-culture strategies on the synthesis of short- and medium-chain fatty acids (SMCFAs) through carbon chain elongation (CCE). The results indicated that the sequential inoculation outperformed simultaneous inoculation in the M. elsdenii and Lactobacillus groups. The inclusion of Lactobacillus significantly enhanced substrate utilization, generating lactate that facilitated the integration of odd carbon carboxylates (such as propionate and valerate) into the CCE products. The caproate concentration in the M. elsdenii+L. pentosus group reached 3.4 g/L, which was 1.3 times that in the control group. Furthermore, the introduction of C. kluyveri effectively boosted the synthesis of butyrate and caproate through CCE using ethanol as an electron donor within the co-culture setup of the M. elsdenii+C. kluyveri group. Moreover, the carbon efficiency of the co-culture group increased by 10–21 % compared to the control group, and the cell protein titer was 1.5–2 times higher than that of the control group. This study has established a method for co-producing SMCFAs and cell proteins utilizing bio-sugars through a co-culture approach, offering implications for lignocellulose utilization and potential high-value applications of SMCFAs in the future.

Microbial Reduction of Solid-Phase Humin by Shewanella oneidensis MR-1 and its Potential Effect on Contaminant Transformation

Insoluble humic substances-humin (HM) are ubiquitous in the environment and often coexist with iron reducers. Previous research has focused on the electron-donating process from HM to iron reducers; however, the reduction process of HM by iron reducers and its impact on the fate of typical contaminants are still poorly understood. In this study, Shewanella oneidensis MR-1 was selected as a model iron reducer, and its ability to reduce HM and the potential environmental impact of bioreduced HM were investigated. The results showed that S. oneidensis MR-1 reduced HMs extracted from different sources to different extents. This process is highly dependent on lactate concentration, salinity, pH, and dissolved oxygen concentration. Alginate bead experiments indicated that the indirect pathway accounted for 40% of the total electrons transferred from S. oneidensis MR-1 to HM. Electrochemical and spectrochemical analyses further revealed that in addition to flavin, c-type cytochrome may mediate electron transfer. The quinone and iron components may be the main functional groups of HM that accept electrons. Finally, we showed that after being reduced by S. oneidensis MR-1, HM can act as an electron donor for microbial nitrate reduction and the chemical reduction of Cr(VI), with electron-mediation efficiencies of 93% and 56%, respectively.

Adaptation mechanisms of Alcanivorax facilitating its predominance in marine environments

IntroductionAlcanivorax, a typical alkane-degrading bacterium, has demonstrated the ability to utilize inorganic electron donor in some reports. However, a comprehensive analysis of its potentiality to utilize inorganic electron donor is still lacking.MethodsIn this study, genomic and phylogenetic analyzes were used to explore the potential oxidative capacity of inorganic compounds in Alcanivorax. And its functions were verified through physiological experiments.ResultsThe sulfur oxidation-related genes sqr and tsdA are prevalent and have various evolutionary origins. Potential genes for CO oxidation were present in 39 strains, whereas genes associated with iron, hydrogen, and ammonia oxidation were either rare or absent. The physiological functions of Sqr and TsdA were confirmed in six representative strains under heterotrophic conditions. Adding thiosulfate enhanced Alcanivorax growth. However, Alcanivorax bacteria perform sulfide detoxification through Sqr rather than by gaining energy via sulfide oxidation Although no strain was confirmed to be chemoautotrophs, we discovered that the two clades, A. xenomutans and A. profundimaris, can grow under conditions with very low organic matter.DiscussionThe ability to utilize inorganic compounds as a supplementary energy source and adapt to carbon oligotrophic growth may contribute to the prevalence of Alcanivorax in marine ecosystems.

Design of highly responsive chemiresistor-based sensors by interfacing NiPc with graphene

Highly sensitive and selective gas-sensing materials are critical for applications ranging from environmental monitoring to breath analysis. A rational approach at the nanoscale is urgent to design next-generation sensing devices. In previous work, we unveiled interesting charge transfer channels at the interface between p-type doped graphene and a layer of nickel phthalocyanine (NiPc) molecules, which we believe could be successfully exploited in gas sensing devices. Here, we have investigated the graphene-NiPc interface’s response to adsorbed gas molecules via first-principles calculations. We focused on NH3 and NO2 as test molecules, representing electron donors and acceptors, respectively. Notably, we identified the Ni dz2 orbital as a key player in mediating the charge transfer and affecting the charge carrier density in graphene. As a proof-of-concept, we then prepared the graphene-NiPc system as a chemiresistor device and exposed it to NH3 and NO2 at room temperature. The sensing tests revealed excellent sensitivity and selectivity, along with a rapid recovery time and a remarkably low detection limit.

Sustainable synthesize of beetroot extract-silver-iron oxide (BE-Ag-Fe2O3) bimetallic nanoparticles for antioxidant studies

In this work, beetroot extract is used to synthesize the silver-iron oxide (Ag-Fe2O3) bimetallic nanoparticles, which are then characterized and used for the antioxidant studies. Phenolic components were found to coat the nanoparticles, according to FT-IR analysis. Tannins and flavonoids in the extract serve as stabilizing and reducing agents. SEM revealed spherical bimetallic nanoparticles that were roughly 40 nm in size. Crystallinity and purity were shown by XRD examination, which also revealed unique reflection peaks. Particle size and zeta potential values clearly confirm that, the prepared bimetallic nanoparticles are in nano size and it is stable in nature. Furthermore, in this study, the antioxidant properties of produced bimetallic nanoparticles are examined, and their efficacy is compared to that of beetroot extract. Beetroot extract-silver-iron oxide (BE-Ag-Fe2O3) bimetallic nanoparticles showed improved radical scavenging effectiveness when compared to DPPH. Moreover, bimetallic nanoparticles demonstrated increased radical scavenging efficacy in relation to DPPH and H2O2. Surprisingly, at 20 mg/ml, the BE-Ag-Fe2O3) bimetallic nanoparticles showed good scavenging activity, reaching 84.65%. The produced bimetallic NPs had greater antioxidant activity than the plant extract, according to an analysis of the total antioxidant capacity and free radical scavenging activity data. Electron donation property of main constituent of beetroot extract was analysed by density functional theory (DFT) and Monte Carlo (MC) simulation. Consequently, this work implies that beetroot extract assisted bimetallic NPs could be a flexible material with a range of uses in the biomedical area.Graphical

The Photodynamic Agent Designed by Involvement of Hydrogen Atom Transfer for Enhancing Photodynamic Therapy.

Although Type-I photodynamic therapy has attracted increasingly growing interest due to its reduced dependence on oxygen, the design of effective Type-I photosensitizers remains a challenge. In this work, we report a design strategy for Type-I photosensitizers by the involvement of hydrogen atom transfer (HAT). As a proof of concept, a HAT-involved Type-I PS, which simultaneously generates superoxide and carbon-centered radicals under light-irradiation, was synthesized. This photosensitizer is comprised of a fluorene-substituted BODIPY unit as an electron acceptor covalently linked with a triphenylamine moiety as an electron donor. Under light-irradiation, photo-induced intramolecular electron transfer occurs to generate the BODIPY anion radical and triphenylamine cation radical. The former transfers electrons to oxygen to generate O2 -⋅, while the latter loses a proton to produce a benzyl carbon-centered radical which is well characterized. The resulting carbon-centered radicals efficiently oxidize NADH by HAT reaction. This photosensitizer demonstrates remarkable photocytotoxicity even under hypoxic conditions, along with outstanding in vivo antitumor efficacy in mouse models bearing HeLa tumors. This work offers a novel strategy for the design of Type-I photosensitizers by involvement of HAT.

Novel Inorganic-Organic Dual-Photosensitizing Dinuclear-Metal Self-Assembly System for Efficient Artificial Photosynthesis without Sacrificial Electron Donors.

Owing to the unique synergistic effect, dinuclear-metal-molecule-catalysts (DMCs) show excellent performance in catalytic fields. However, for overall photocatalytic CO2 reaction (CO2RR), it is still a challenge to construct well-matched photosensitizer (PS) components for DMCs-based photocatalysts. Inorganic-quantum-dot PS possesses capacities of multiple exciton generation and catalyzing water oxidation but is incompatible with DMCs. In contrast, organic PS can be covalently linked with DMCs but inescapable of using sacrificial electron donors. For overall photocatalytic CO2RR, organic-inorganic dual-photosensitizing system might be a promising candidate. Herein, we employed covalent-linking and electrostatic-driven approaches to construct the self-assembly of pyrene-sensitized Co2L DMCs (Py-Co2L) and perovskite (PVK) quantum dots, i.e., PVK@[Py-Co2L]. Using H2O as an electron donor, PVK@[Py-Co2L] realized 105.24 μmol ⋅ g-1⋅h-1 CO yield in photocatalytic CO2RR, much higher than PVK (15.44 μmol ⋅ g-1⋅h-1) and PVK@Co2L (32.30 μmol ⋅ g-1 ⋅ h-1), ascribing to the efficient photogenerated charge separation and transfer. The experimental results and theoretical investigations demonstrated that the pyrene linked on Co2L boosted the electron delivery from PVK to DMCs. Besides, this strategy could also be extended to the photocatalytic H2 evolution coupled with alcohol oxidation. As a proof-of-concept, our work lightens the integration of DMCs, organic and inorganic PS components, promoting the development of photocatalysis without sacrificial electron donors.

The Photodynamic Agent Designed by Involvement of Hydrogen Atom Transfer for Enhancing Photodynamic Therapy

AbstractAlthough Type‐I photodynamic therapy has attracted increasingly growing interest due to its reduced dependence on oxygen, the design of effective Type‐I photosensitizers remains a challenge. In this work, we report a design strategy for Type‐I photosensitizers by the involvement of hydrogen atom transfer (HAT). As a proof of concept, a HAT‐involved Type‐I PS, which simultaneously generates superoxide and carbon‐centered radicals under light‐irradiation, was synthesized. This photosensitizer is comprised of a fluorene‐substituted BODIPY unit as an electron acceptor covalently linked with a triphenylamine moiety as an electron donor. Under light‐irradiation, photo‐induced intramolecular electron transfer occurs to generate the BODIPY anion radical and triphenylamine cation radical. The former transfers electrons to oxygen to generate O2−⋅, while the latter loses a proton to produce a benzyl carbon‐centered radical which is well characterized. The resulting carbon‐centered radicals efficiently oxidize NADH by HAT reaction. This photosensitizer demonstrates remarkable photocytotoxicity even under hypoxic conditions, along with outstanding in vivo antitumor efficacy in mouse models bearing HeLa tumors. This work offers a novel strategy for the design of Type‐I photosensitizers by involvement of HAT.

Novel Inorganic‐Organic Dual‐Photosensitizing Dinuclear‐Metal Self‐Assembly System for Efficient Artificial Photosynthesis without Sacrificial Electron Donors

AbstractOwing to the unique synergistic effect, dinuclear‐metal‐molecule‐catalysts (DMCs) show excellent performance in catalytic fields. However, for overall photocatalytic CO2 reaction (CO2RR), it is still a challenge to construct well‐matched photosensitizer (PS) components for DMCs‐based photocatalysts. Inorganic‐quantum‐dot PS possesses capacities of multiple exciton generation and catalyzing water oxidation but is incompatible with DMCs. In contrast, organic PS can be covalently linked with DMCs but inescapable of using sacrificial electron donors. For overall photocatalytic CO2RR, organic–inorganic dual‐photosensitizing system might be a promising candidate. Herein, we employed covalent‐linking and electrostatic‐driven approaches to construct the self‐assembly of pyrene‐sensitized Co2L DMCs (Py‐Co2L) and perovskite (PVK) quantum dots, i.e., PVK@[Py‐Co2L]. Using H2O as an electron donor, PVK@[Py‐Co2L] realized 105.24 μmol ⋅ g−1⋅h−1 CO yield in photocatalytic CO2RR, much higher than PVK (15.44 μmol ⋅ g−1⋅h−1) and PVK@Co2L (32.30 μmol ⋅ g−1 ⋅ h−1), ascribing to the efficient photogenerated charge separation and transfer. The experimental results and theoretical investigations demonstrated that the pyrene linked on Co2L boosted the electron delivery from PVK to DMCs. Besides, this strategy could also be extended to the photocatalytic H2 evolution coupled with alcohol oxidation. As a proof‐of‐concept, our work lightens the integration of DMCs, organic and inorganic PS components, promoting the development of photocatalysis without sacrificial electron donors.

Design and Development of D-A-D Organic Material for Solution-Processed Organic/Si Hybrid Solar Cells with 17.5% Power Conversion Efficiency.

Organic/silicon hybrid solar cells have attracted much interest due to their cheap fabrication process and simple device structure. A category of organic substances, Dibenzothiophene-Spirobifluorene-Dithiophene (DBBT-mTPA-DBT), comprises dibenzo [d,b] thiophene and 3-(3-methoxyphenyl)-6-(4-methoxyphenyl)-9H-Carbazole, which function as electron donors. In contrast, methanone is an electron acceptor, with an ∆Est of 3.19 eV. This work focused on hybrid solar cells based on the guest-host phenomena of DBBT-mTPA-DBT and CBP. Using a Si/poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT: PSS) hybrid solar cell with an ultra-thin Dibenzothiophene-Spirobifluorene-Dithienothiophene (DBBT-mTPA-DBT) interlayer between Si and Al led to a PCE of 17.5 ± 2.5%. The DBBT-mTPA-DBT interlayer substantially improved the Si/Al interface, reducing contact resistance from 6.5 × 10⁻1 Ω·cm2 to 3.5 × 10⁻2 Ω·cm2. This improvement increases electron transport efficiency from silicon to aluminum and reduces carrier recombination. The solar cell containing the DBBT-mTPA-DBT/Al double-layer cathode shows a 10.85% increase in power conversion efficiency relative to the standard Al cathode device.

Graphene Oxide-Doped Indium Oxide Buffer Film Sandwiched between Titanium Oxide Layers for the Development of Photosensitive Resistive Memory Devices.

Over the past decade, metal oxide semiconductors have attracted considerable attention because of their transparency, high intrinsic charge carrier mobility, and charge carrier density. Metal oxide semiconductors also provide a promising route to develop resistive memory devices because of the tunability of their conductivity via the removal of oxygen ions, forming oxygen vacancies that can act as electron donors. Here, this paper reports the fabrication of a resistive random-access memory (ReRAM) device with TiO2 and TiO2-x layers and introduces a solution-processed In2O3-graphene oxide (GO) buffer layer from a water-based precursor solution to tune the switching characteristics. The devices were compared with a ReRAM device with no buffer layer, and the device composition was optimized by tuning the GO concentration in the layers. The devices showed hysteresis under cyclically scanned bias between positive and negative voltages with clear switching between the low resistance state (LRS) and the high resistance state (HRS). The optimized device also showed a more than 3 orders of magnitude difference in resistance between the LRS and HRS and a stable current retention. The devices also showed photoresponsive behaviors. In the LRS, the current increased significantly under illumination, while in the HRS, the current deteriorated slowly when constantly illuminated. These results highlight the dual role of the GO flakes in the buffer layer by increasing the resistance in the HRS and providing a photoresponsive switching capability. The ReRAM device was connected to a TFT device, and its feasibility as a memory component in a digital circuit was successfully demonstrated. These results provide a new avenue for developing metal-oxide-based ReRAM devices with GO-containing active layers.

Self-cleaned surface of vanadium boride for long-lasting and boosted Fenton oxidation

Coupling extra electron supply with iron-mediated advanced oxidation processes (AOPs) is an efficient strategy for long-lasting oxidation of organic contaminants in environmental remediation. Many subsequent attempts have been made, such as homogeneous catalysts and metal catalysts, of which secondary organic pollution and surface passivation layers limit their application. In this work, metal borides as co-catalysts can efficiently accelerate the Fenton reaction by firmly sacrificing electrons to Fe(III) reduction. Among multiple metallic borides, vanadium boride (VB2) performs superiorly as dual active sites to solve the Fe(III) cycle dilemma and quickly generate hydroxyl radicals via Fenton reaction for almost completely eliminating almost carbamazepine (CBZ) in VB2/Fe(III)/H2O2. Characterization analysis and the density functional theory (DFT) calculation unveil that the synergistic effect of V and B on the surface of VB2 makes Fe-O bonds of FeOH2+ weaker (from 173.8 pm to 178.4 pm) to produce more active Fe(III) species. And meanwhile, active Fe(III) can be rapidly reduced into Fe(II) on the surface of VB2 and then be completely released into solution for subsequent Fenton reaction and hydroxyl radical generation. More importantly, VB2 performs steadily and efficiently for 7th consecutive test in VB2/Fe(III)/H2O2 to degrade more than 95% CBZ, resulting from the self-cleaning surface of VB2 to expose reactive regions for persistent electron sacrifice and sustainably stimulative Fenton oxidation. Therefore, this research offers the detailed fundamental perception into the genesis of VB2 as well as a novel electron donor for boosting Fenton oxidation towards water remediation.

PTB7-Th sensitized by AA-CDs for photoelectrochemical protein assay

In this work, a novel photoelectrochemical (PEC) aptasensor for C-reactive protein (CRP) assay was successfully constructed by using poly{4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b,4,5-b′]dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4–b]-thiophene-4,6-diyl} (PTB7-Th) as the photoactive substrate and carbon dots modified with amino acid (AA-CDs) as the signal sensitizer. Impressively, the designed AA-CDs/PTB7-Th sensitized structure presented a strong and stable photocurrent response without any external electron donor, which was mainly derived from the inherent self-supplied electron characteristic of PTB7-Th and the high sensitizing effect of AA-CDs towards PTB7-Th. The obtained PEC signal produced from the AA-CDs/PTB7-Th sensitized structure was even larger than the sum of PTB7-Th and AA-CDs. Besides, the special recognition between CRP and its aptamer endowed the PEC aptasensor with excellent specificity, suggesting that the PEC aptasensing platform embraced strong anti-interference ability. Accordingly, the PEC aptasensor fabricated here confirmed a detection limit (LOD) of 0.33 pg/mL for CRP assay within the detection range of 1 pg/mL to 1 µg/mL. Importantly, this system offered an ideal PEC aptamer sensing platform based on the AA-CDs/PTB7-Th sensitized structure for CRP determination, laying the foundation for its application in the detection of real protein samples.

Stereoselective Radical Acylfluoroalkylation of Bicyclobutanes via N-Heterocyclic Carbene Catalysis.

Cyclobutanes are prominent structural components in natural products and drug molecules. With the advent of strain-release-driven synthesis, ring-opening reactions of bicyclo[1.1.0]butanes (BCBs) provide an attractive pathway to construct these three-dimensional structures. However, the stereoselective difunctionalization of the central C-C σ-bonds remains challenging. Reported herein is a covalent-based organocatalytic strategy that exploits radical NHC catalysis to achieve diastereoselective acylfluoroalkylation of BCBs under mild conditions. The Breslow enolate acts as a single electron donor and provides an NHC-bound ketyl radical with appropriate steric hindrance, which effectively distinguishes between the two faces of transient cyclobutyl radicals. This operationally simple method tolerates various fluoroalkyl reagents and common functional groups, providing a straightforward access to polysubstituted cyclobutanes (75 examples, up to >19:1 d.r.). The combined experimental and theoretical investigations of this organocatalytic system confirm the formation of the NHC-derived radical and provide an understanding of how stereoselective radical-radical coupling occurs.

Modification of cobalt bis(dicarbollide) ions with nitrile groups on carbon atoms: a unique low-temperature skeletal rearrangement due to the specific electron-donor character of CN substitution.

Herein, we report on the synthesis and stereochemistry of mono- and isomeric dinitrile derivatives of [(1,2-C2B9H11)2-3,3'-Co]- ions. The shape and electronic properties of CN groups can apparently surmount the strain associated with the substitution of two vicinal carbon positions. Owing to electron donation to the cage, this results in a substituent-induced rearrangement of one of the carbon atoms to the upper pentagonal ring. The molecular structure of this isomer was confirmed using sc-XRD and DFT chemical computations.