Strong Electron-withdrawing Group Research Articles

The mechanism and origins of the chemo- and regio-selectivity of ruthenium porphyrin catalyzed C[sbnd]H bonds oxidation

Selective functionalization of polymers derived from branched alkane monomers is extremely challenging due to the low reactivity of CH bonds and uncontrolled depolymerization. In this work, the chemoselective and regioselective catalytic oxygenation mechanism of hydrocarbons with ruthenium porphyrin complexes and aromatic N-oxides was investigated by density functional theory (DFT) calculations. The results revealed that the oxoruthenium porphyrin species with remarkable reactivity as oxygen transfer agents is responsible for the hydrogen abstraction from CH bonds followed by fast hydroxyl radical rebound. Details regarding the calculations of various oxidation processes show that the regioselectivity is related to the intrinsic strength of different CH bonds in branched alkanes and the charge transfer of the hydrogen atom transfer (HAT) step. Comparing the oxidations of branched alkanes to alcohols and ketones, the chemoselectivity is attributed to the relative barriers of HAT pathways in the two-step oxidation stage. Finally, the substituent effects of fluorine in the porphyrin ligand are elucidated and a stronger electron-withdrawing group is predicted to promote the HAT process and regulate hydroxyl radical rebound, ultimately enabling more efficient oxidation. These findings provide relevant information for understanding the selective oxidation of polyolefins through transition metal catalysis and enzymatic catalysis.

Functionalized Phenanthrene Imide-Based Polymers for n-Type Organic Thin-Film Transistors.

High-performing n-type polymers are crucial for the advance of organic electronics field, however strong electron-deficient building blocks with optimized physicochemical properties for constructing them are still limited. The imide-functionalized polycyclic aromatic hydrocarbons (PAHs) with extended π-conjugated framework, high electron deficiency and good solubility serve as promising candidates for developing high-performance n-type polymers. Among the PAHs, phenanthrene (PhA) features a well-delocalized aromatic π-system with multiple modifiable active sites . However, the PhA-based imides are seldom studied, mainly attributed to the synthetic challenge. Herein, we report two functionalized PhAs, CPOI and CPCNI, by simultaneously incorporating imide with carbonyl or dicyanomethylene onto PhA. Notably, the dicyanomethylene-modified CPCNI exhibits a well stabilized LUMO energy level (-3.84 eV), attributed to the synergetic inductive effect from imide and cyano groups. Subsequently, based on CPOI and CPCNI, two polymers PCPOI-Tz and PCPCNI-Tz were developed. Applied to organic thin-film transistors, owing to the strong electron-deficiency of CPCNI, polymer PCPCNI-Tz shows an improved electron mobility and largely decreased threshold voltage compared with PCPOI-Tz. This work affords two structurally novel electron-deficient building blocks and highlights the effectiveness of dual functionalization of PhAs with strong electron-withdrawing groups for devising n-type polymers.

Preparation and Properties of Mechanically Robust, Colorless, and Transparent Aramid Films.

In this study, various diamine monomers were used to synthesize aramid polymer films via a low-temperature solution condensation reaction with diacid chloride. For diamines with relatively high basicity, the reaction system became opaque because amine salt formation inhibited polymer synthesis. Meanwhile, low-basicity diamines with strong electron-withdrawing groups, such as CF3 and sulfone, were smoothly polymerized without amine salt formation to provide highly viscous solutions. The acid byproduct HCl generated during polymerization was removed by adding propylene oxide to the reaction vessel and converting the acid into highly volatile inert substances. The resulting solutions were used as varnishes without any additional purification, and polymer films with an excellent appearance were easily obtained through a conventional casting and convection drying process. The films neither tore nor broke when pulled or bent by hand; furthermore, even when heated up to 400 °C, they did not decompose or melt. Moreover, polymers prepared from 2,2-bis(trifluoromethyl)benzidine (TFMB) and bis(4-aminophenyl)sulfone (pAPS) did not exhibit glass transition until decomposition. The prepared polymer films showed a high elastic modulus of more than 4.1 GPa and a high tensile strength of more than 52 MPa. In particular, TFMB-, pAPS-, and 2,2-bis(4-aminophenyl)hexafluoropropane-based polymer films were colorless and transparent, with very high light transmittances of 95%, 96%, and 91%, respectively, at 420 nm and low yellow indexes of 2.4, 1.9, and 4.3, respectively.

Defect and nanostructure engineering of polymeric carbon nitride for visible-light-driven CO2 reduction

Sunlight-induced photocatalytic carbon dioxide (CO2) reduction to energy-rich chemicals by metal-free polymeric carbon nitride (CN) semiconductor is a promising tactic for sustained solar fuel production. However, the reaction efficiency of CO2 photoreduction is restrained seriously by the rapid recombination of photogenerated carriers on CN polymer. Herein, we incorporate 2-aminopyridine molecule with strong electron-withdrawing group into the skeleton edge of CN layers through a facile one-pot thermal polymerization strategy using urea as the precursor, which renders a modified carbon nitride (ACN) with extended optical harvesting, abundant nitrogen defects and ultrathin nanosheet structure. Consequently, the ACN photocatalyst with desirable structural features attains enhanced separation and migration of photoexcited charge carriers. Under visible light irradiation with Co(bpy)32+ as a cocatalyst, the optimized ACN sample manifests a high CO2 deoxygnative reduction activity and high stability, providing a CO yielding rate of 17 μmol h−1, which is significantly higher than that of pristine CN. The key intermediates engaged in CO2 photoreduction reaction are determined by the in situ diffuse reflectance infrared Fourier transform spectroscopy, which sponsors the construction of the possible photocatalytic CO2 reduction mechanism on ACN nanosheets.

Investigating the Effects of Fluorine Substituents on Organic Dyes in Dye-Sensitized Solar Cells

We synthesized and evaluated five organic dyes that featured both mono- and di-substituted fluorine atoms for application in dye-sensitized solar cells (DSSCs). The dye structure was designed with N, N-dimethylaniline as a donor, fluorophenyl as an π-conjugated bridge, and cyanoacetic acid as an anchoring and acceptor group. The fluorine substituents are strong electron-withdrawing groups, introducing different numbers and positions of fluorine atoms (ortho and meta) that were expected to the ability of the acceptor parts of the dye. The results showed that adding the fluorine mono-substitution in the ortho position can enhance the efficiency of the solar cells in comparison with the meta-substitution and unsubstituted one. However, the di-substitution by fluorine atoms in two ortho positions and ortho, meta positions reduced the performance of the solar cells. The reason was related to the effect of π-conjugation between the fluorine substituent and the carbonyl group of the carboxylic acid. The DSSCs based on dye 14 achieved the best results with power conversion efficiency (PCE) = 3.33%, (Jsc = 5.43 mA cm-2, Voc = 0.81V and FF = 75.85%) under standard conditions with I3-/I- as the electrolyte.

Nanoconfined catalytic membrane assembled by nitrogen-doped carbon encapsulating Fe-based nanoparticles for rapid removal of 2,4-dichlorophenol in wastewater by peroxymonosulfate activation

Surface-dependent non-radical oxidation of carbon materials-based persulfate systems show a better application prospect in the removal of pollutants in complex wastewater. However, their potential is severely limited by the restricted liquid-to-solid mass transfer efficiency of conventional suspension systems. In this paper, a nitrogen-doped carbon encapsulating iron-based nanoparticles (Fe@NC) was prepared, and loaded onto a polyvinylidene fluoride (PVDF) membrane to construct a novel catalytic membrane Fe@NC/PVDF. The Fe@NC/PVDF/PMS system could achieve 99.74% of 2,4-dicholophenol (2,4-DCP) removal within a retention time of 0.867 s, the kinetic constant is 840 times higher than that of Fe@NC/PMS system, and 2–5 orders of magnitude higher than that of various reported advanced oxidation processes systems. The system exhibits strong anti-interference to various water matrices, long-time operational stability at high flux (306 L·m−2·h−1), universality to pollutants that do not contain strong electron-withdrawing groups and mitigation of membrane fouling. Mechanism studies indicate that the electron transfer pathway dominates the 2,4-DCP removal, and singlet oxygen (1O2) plays an auxiliary role. The higher mass transfer efficiency of the filtration mode releases the full potential of the non-radical pathway. This paper provides theoretical and technical support for the development and efficient utilization of carbon-based materials with excellent persulfate catalytic properties.

Metal-Free, Hindered, Regioselective Access to Multifunctional Groups Diarylamines via SN Ar Substitution of P-Nitroso Aromatic Methyl Ether by Arylamines.

Multifunctional groups diarylamines, an innovative product, efficiently produced from arylamines and p-nitrosoanisole derivatives by intermolecular SN Ar under weak acid conditions. This SN Ar proceeds under mild reaction conditions, and more significantly, the substrates involved do not necessarily require strong electron-withdrawing groups. Moreover, this SN Ar is characterized by resistance to space crowding, tolerance to halogen and nitroso functional groups, and high regioselectivity. Mechanistic observations suggest that the SN Ar is the result of the transfer of the positive charge center of the protonated nitroso group to the p-methoxy group.

The meso-substituent electronic effect of Fe porphyrins on the electrocatalytic CO2 reduction reaction.

We report Fe porphyrins bearing different meso-substituents for the electrocatalytic CO2 reduction reaction (CO2RR). By replacing two and four meso-phenyl groups of Fe tetraphenylporphyrin (FeTPP) with strong electron-withdrawing pentafluorophenyl groups, we synthesized FeF10TPP and FeF20TPP, respectively. We showed that FeTPP and FeF10TPP are active and selective for CO2-to-CO conversion in dimethylformamide with the former being more active, but FeF20TPP catalyzes hydrogen evolution rather than the CO2RR under the same conditions. Experimental and theoretical studies revealed that with more electron-withdrawing meso-substituents, the Fe center becomes electron-deficient and it becomes difficult for it to bind a CO2 molecule in its formal Fe0 state. This work is significant to illustrate the electronic effects of catalysts on binding and activating CO2 molecules and provide fundamental knowledge for the design of new CO2RR catalysts.

Directed nucleophilic aromatic substitution reaction.

In this study, we discovered a directed nucleophilic aromatic substitution reaction, "directed SNAr (dSNAr)," in the reaction of ortho-iodobezamides and amine in the presence of pyridine. The reaction proceeded ortho-specifically and did not require a strong electron-withdrawing group on the arene substrate. Most reactions proceeded at room temperature in the presence of Py, and a wide range of amine nucleophiles can be applied. Furthermore, the reactions with benzamide substituted with multiple halogens were found to be 100% ortho-selective.

Degradation of neonicotinoids with different molecular structures in heterogeneous peroxymonosulfate activation system through different oxidation pathways

The elimination of neonicotinoids (NEOs) from water has been a research priority due to their threats to human health and ecosystems. In this study, we established the heterogeneous peroxymonosulfate (PMS) activation system using manganese catalyst (Mn NC) and cobalt catalyst (Co NC) to trigger the nonradical oxidation and synergistic oxidation pathway, respectively to remove NEOs. The results showed that the nonradical oxidation system exhibited superior NEOs degradation capability. The composition of organic pollutants in wastewater significantly impacted subsequent degradation processes. The charge distribution and reaction sites of various NEOs were analyzed using density functional theory (DFT) calculations, and it demonstrated the electron distribution and activity of NEOs were significantly influenced by the type and number of substituents. Nitro group (–NO2) and cyanide group (–CN) were identified as strong electron-withdrawing groups and prone to be attacked by negatively charged radicals. The transformation of NEOs was analyzed, and result showed that the C and N sites adjacent to the nitro group and cyanide group were more susceptible to oxidation attacks. S and N atoms, which possess strong electronegativity and high electron cloud density, were identified as key active sites in the degradation pathway. The outcomes of this study provide valuable guidance for the oriented regulation of oxidation pathways towards efficient removal of NEOs in water.

Mechanism Study of Molecular Trap in All-Organic Polystyrene-Based Dielectric Composite.

It is a huge challenge to explore how charge traps affect the electric breakdown of polymer-based dielectric composites. In this paper, alkane and aromatic molecules with different substituents are investigated according to DFT theoretical method. The combination of strong electron-withdrawing groups and aromatic rings can establish high electron affinity molecules. 4'-Nitro-4-dimethylaminoazobenzene (NAABZ) with a vertical electron affinity of 1.39eV and a dipole moment of 10.15 D is introduced into polystyrene (PSt) to analyze the influence of charge traps on electric properties. Marcus charge transfer theory is applied to calculate the charge transfer rate between PSt and NAABZ. The nature of charge traps is elaborated from a dynamic perspective. The enhanced breakdown mechanism of polymers-based composites stems from the constraint of carrier mobility caused by the change in transfer rate. But the electrophile nature of high electron affinity filler can decrease the potential barriers at the metal-polymer interface. Simultaneously, the relationship between the electron affinity of fillers and the breakdown strength of polymer-based composites is nonlinear because of the presence of the inversion region. Based on the deep understanding of the molecular trap, this work provides the theoretical calculation for the design and development of high-performance polymer dielectrics.

3+2]-Cycloaddition of Nitrile Imines to Parabanic Acid Derivatives-An Approach to Novel Spiroimidazolidinediones.

Approximately 1,3-Dipolar cycloaddition of imidazolidine derivatives containing exocyclic double bonds is a convenient method of creating spiro-conjugated molecules with promising anticancer activity. In this work, the derivatives of parabanic acid (2-thioxoimidazolidine-4,5-diones and 5-aryliminoimidazolidine-2,4-diones) were first investigated as dipolarophiles in the reactions with nitrile imines. The generation of nitrile imines was carried out either by the addition of tertiary amine to hydrazonoyl chlorides «drop by drop» or using the recently proposed diffusion mixing technique, which led to ~5-15% increases in target compound yields. It was found that the addition of nitrile imines to C=S or C=N exocyclic double bonds led to 1,2,4-thiazolines or triazolines and occurred regioselectively in accordance with the ratio of FMO coefficients of reactants. The yield of the resulting spiro-compound depended on the presence of alkyl substituents in the nitrile imine structure and was significantly decreased in reactions with imines with strong electron donor or electron-withdrawing groups. Some of the obtained compounds showed reasonable in vitro cytotoxicity. IC50 values were calculated for HCT116 (colon cancer) cells using the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) test.

Exploring Structural-Photophysical Property Relationships in Mitochondria-Targeted Deep-Red/NIR-Emitting Coumarins.

Organic fluorophores operating in the optical window of biological tissues, namely in the deep-red and near-infrared (NIR) region of the electromagnetic spectrum, offer several advantages for fluorescence bioimaging applications owing to the appealing features of long-wavelength light, such as deep tissue penetration, lack of toxicity, low scattering, and reduced interference with cellular autofluorescence. Among these, COUPY dyes based on non-conventional coumarin scaffolds display suitable photophysical properties and efficient cellular uptake, with a tendency to accumulate primarily in mitochondria, which renders them suitable probes for bioimaging purposes. In this study, we have explored how the photophysical properties and subcellular localization of COUPY fluorophores can be modulated through the modification of the coumarin backbone. While the introduction of a strong electron-withdrawing group, such as the trifluoromethyl group, at position 4 resulted in an exceptional photostability and a remarkable redshift in the absorption and emission maxima when combined with a julolidine ring replacing the N,N-dialkylaminobenzene moiety, the incorporation of a cyano group at position 3 dramatically reduced the brightness of the resulting fluorophore. Interestingly, confocal microscopy studies in living HeLa cells revealed that the 1,1,7,7-tetramethyl julolidine-containing derivatives accumulated in the mitochondria with much higher specificity. Overall, our results provide valuable insights for the design and optimization of new COUPY dyes operating in the deep-red/NIR region.

Morphology study of light– and pH–responsive amphiphiles with DSA for detection of nitrobenzene derivatives

Supramolecular molecular self–assemblies with 9, 10-distyrylanthracene (DSA) frameworks have good application prospects in fluorescent probes and optical materials owing to the unique AIE effect of the DSA unit. In this study, amphiphilic rod–coil molecules with rigid DSA parts and flexible oligoether chains were designed and synthesised, and their assembly capacities were investigated. The amphiphilic molecule with a lateral methyl unit in the coil branch formed worm–like supramolecular assemblies, while the molecule without lateral group self–assembled into an interwoven ribbon like structure in aqueous solution. This is due to noncovalent molecular interactions, such as the π–π stacking interaction of the rigid segments for the former or the hydrophilic–hydrophobic effect of molecules in the aqueous solution for the latter. Interestingly, under irradiation with 365 nm UV light, the original UV absorption of the molecule decreased and fluorescence quenching occurred, accompanied by a decrease in the size of the original aggregates, which became more apparent with as irradiation time increased, indicating the presence of photo-degradation. These molecular morphologies were also significantly influenced by the pH of the aqueous solution and produced nanoparticles of various sizes. Furthermore, we investigated the adsorption capacity of nitro compounds and found that molecular aggregates could be used for the detection of nitroaromatic compounds with strong electron-withdrawing groups.

Facile synthesis of functionalized polysiloxanes with nonconventional fluorescence by oxa-Michael addition reaction

ABSTRACTDeveloping a novel methodology for the synthesis of functionalized polysiloxanes is highly desirable because of their extensive applications in engineering, textile, construction, electronics, and medical systems. Herein we introduce the oxa-Michael addition reaction as an efficient methodology to prepare a series of functionalized polysiloxanes from hydroxyalkyl-containing polysiloxanes and vinyl monomers using phosphazene base as the catalyst. The effects of various factors, including reaction time, feed ratio and solvent, were explored in this reaction. It was found that the reaction can be carried out under mild reaction (room temperature in 6 h to 24 h) with moderate to high conversion yields (60% to 99%). In particular, vinyl monomers with strong electron-withdrawing groups (e.g., cyano and sulfone groups) have higher reactivity, and the functionalized polysiloxanes can be obtained quantitatively or near-quantitatively. Interestingly, their molecular weights determined by gel permeation chromatography (GPC) reveal that the Si-O-Si skeletons were attacked by phosphazene base and re-arranged during the reaction, thus leading to improved molecular weights and more uniform molecular weight distributions in the final products than the original polysiloxanes. Moreover, these polysiloxanes exhibited intriguing nonconventional fluorescence due to the presence of unique chromophores, and those containing cyano and sulfone groups particularly exhibit the best fluorescence performance. More organosilicon materials could be developed under this simple strategy.

Rational design synthesis and evaluation of a novel near-infrared fluorescent probe for selective imaging of amyloid-β aggregates in Alzheimer's disease

Alzheimer's disease (AD) is a degenerative neurological disorder that remains incurable to date, seriously affecting the quality of life and health of those affected. One of the key neuropathological hallmarks of AD is the formation of amyloid-β (Aβ) plaques. Near-infrared (NIR) probes that possess a large Stokes shift show great potential for imaging of Aβ plaques in vivo and in vitro. Herein, we proposed a rational strategy for design and synthesis of a series of NIR fluorescent probes that incorporate a tricarbonitrile group as a strong electron-withdrawing group (EWG) to enable NIR emission and large Stokes shift for optimal imaging of Aβ plaques. The probe TCM-UM exhibited remarkable in vitro performance, including strong NIR emission (λem = 670 nm), large Stokes shift (120–245 nm), and its affinity for Aβ42 aggregates (Kd = 43.78 ± 4.09 nM) was superior to the commercially available probe Thioflavin T (ThT, Kd = 896.04 ± 33.43 nM). Further, TCM-UM was selected for imaging Aβ plaques in brain tissue slices and APP/PS1 transgenic (AD) mice, the results indicated that TCM-UM had an excellent ability to penetrate the blood-brain barrier (BBB) compared with ThT, and it could effectively distinguish wild-type (Wt) mice and APP/PS1 transgenic (AD) mice.

A rationalization for the structure‒activity relationship of α-functionalized β-enamino γ-sultams

Herein we describe the reaction of 2-methyl-2-(methylamino)propanenitrile and 1-(methylamino)cyclobutane-1-carbonitrile with α-functionalized sulfonyl chlorides and the reactivity of resulting α-functionalized β-enamino γ-sultams. The nature of the substituent or the functional group in the α-position has a decisive impact on the reactivity of β-enamino γ-sultams. In particular, α-unsubstituted β-enamino γ-sultams and those possessing either electron-donating substituents or phenyl group are prepared through the two-step procedure and are prone to acid-mediated hydrolysis. Contrary to that, a strong electron-withdrawing group in the α-position enables the synthesis of the corresponding β-enamino γ-sultams in a one-pot manner and makes them tolerate the acid-mediated hydrolysis. The analysis of the results of a complex study involving physical methods (NMR and IR spectroscopy, X-ray diffraction study) and DFT calculations (performed at PBE0 QZVP level of theory) allowed us to rationalize and formulate the rules of structure‒activity relationship for the discussed sultams. It turned out, that the simplest way to predict the reactivity of α-functionalized β-enamino γ-sultams is the 1H NMR spectroscopy: if the NH2 group appears in the spectrum as a two-proton singlet the compound is highly likely can be further modified while the appearance of two separated one-proton singlets indicates a low reactivity of β-enamino γ-sultams.

The anticancer/cytotoxic effect of a novel gallic acid derivative in non-small cell lung carcinoma A549 cells and peripheral blood mononuclear cells from healthy individuals and lung cancer patients.

Gallic acid (GA) is a naturally occurring polyphenol with a strong antioxidant capacity. GA stimulates the apoptosis of cancer cells, thereby suppressing cancer cell invasion. However, the low oral permeability of GA limits its therapeutic use. In order to enhance the antioxidant capacity and oral permeability of GA, a series of compounds analogous to GA were synthesized: 4-methoxybenzenesulfonamide (MBS), 3,4-dimethoxybenzenesulfonamide (DMBS) and 3,4,5-trimethoxybenzenesulfonamide (TMBS). In the new compounds, hydroxyl groups were replaced with various numbers of methoxy groups (stronger electron-donating groups), to increase hydrophobicity and oral permeability compared to GA. In addition, the carboxylic group was replaced with a sulfonyl group (a stronger electron-withdrawing group), to increase the molecular polarity and antioxidative activities of the compounds. The cell counting kit-8 (CCK-8) assay was used to detect the effect of GA, MBS, DMBS, and TMBS on cell proliferation and apoptosis in peripheral blood mononuclear cells (PBMCs) from healthy individuals and non-small cell lung carcinoma A549 cells. Additionally, the comet assay was used to assess the genotoxicity of these compounds in PBMCs from healthy individuals, lung cancer patients, and A549 cells. Compared to untreated cells, TMBS reduced DNA damage more effectively than GA in PBMCs from lung cancer patients and healthy donors. Furthermore, in comparison to GA, TMBS was more cytotoxic in A549 cells. Moreover, TMBS was not cytotoxic in healthy PBMCs, suggesting that TMBS demonstrates therapeutic potential in cancer.

Designing a high-potential metal-free viologen-based redox polymer for effective wiring of FAD-dependent glucose dehydrogenase

Metal-free organic redox mediators, whose redox potentials can be tuned according to the intended enzyme system and application, are emerging as alternative mediators for the design of improved enzyme-based biosensors and biofuel cells. We report a novel class of metal-free redox polymer containing a polymer-tethered dicyano viologen mediator for the immobilization of FAD-dependent glucose dehydrogenase (FAD-GDH) on graphite electrodes. Incorporation of strong electron-withdrawing cyano groups to the viologen moiety ensures the formation of high potential viologen-based redox polymer with an envisaged pH-independent redox potential close to 50 mV (vs Ag /AgCl/ 3 M KCl) and a negligible impact on oxygen reduction. The bioelectrode comprising of newly designed redox polymer and FAD-GDH showed enhanced electrocatalytic activity in the presence of glucose, confirming effective wiring of FAD-GDH, if embedded within the redox polymer.

Synthesis and Characterization of Octacyano-Fe-Phthalocyanine.

Octacyano-metal-phthalocyanine MPc(CN)8 is a promising n-type stable organic semiconductor material with eight cyano groups, including a strong electron-withdrawing group at its molecular terminals. However, a thorough investigation of MPc(CN)8 has not yet been conducted. Therefore, we synthesized FePc(CN)8 and investigated its crystal structure, chemical and electronic states, electrical properties, photocatalytic activity, and magnetic properties. In this paper, we discuss the various properties of MPc(CN)8 in comparison with those of FePc. X-ray diffraction measurements indicated that the crystal structure of FePc(CN)8 was strongly influenced by the cyano groups and differed from the α- and β-forms of FePc. The space group P4/mcc structure of FePc(CN)8 was similar to that of the x-form of LiPc. The ultraviolet-visible (UV-vis) absorption spectrum of FePc(CN)8 was observed at wavelengths longer than that of FePc. Density functional theory-based molecular orbital calculations indicated that the energy gap of FePc(CN)8 is smaller than that of FePc, which can lead to the observation of the Q-band in the UV-vis absorption spectrum of FePc(CN)8 at longer wavelengths than that of FePc. Because FePc(CN)8 has a wider optical absorption band in the visible region than FePc, its photocatalytic activity is approximately four times higher than that of FePc. The conductivity of FePc(CN)8 was also higher than that of FePc, which is due to the larger overlap of π-electron clouds of the molecules in the crystal structure of FePc(CN)8. Magnetic measurements revealed that FePc(CN)8 exists in an antiferromagnetic ground state. The magnetic properties of FePc(CN)8 are specific to its crystal structure, with direct exchange interactions between Fe2+ ions and π-electron-mediated interactions. In particular, the Pauli paramagnetic behavior at high temperatures and the antiferromagnetic behavior at low temperatures (Weiss temperature θ = -4.3 ± 0.1 K) are characteristic of the π-d system.