Spectrometric monitoring of CO2 electrolysis on a molecularly modified copper surface.

Since copper has been extensively studied due to its unique ability to reduce carbon dioxide to hydrocarbons and alcohols, it tends to yield a mixture of products. Among various efforts to improve the selectivity and efficiency of this catalysis, the introduction of organic molecules and polymers on the copper/electrolyte interface has proven to be an effective and promising way to improve surface activity, considering the variation and precise designability of organic structures. The role of surface molecular modifiers, however, is not as simple as that in homogeneous catalysts, and an understanding of a wide scale of interactions from the atomic scale to the whole electrode structure is required. This feature article classifies those different scale interactions caused by organic modifiers on copper catalysts, together with the experimental support by in situ vibrational spectroscopy which directly observes surface species and events. Based on these recent understandings, novel fabrication methods of organic structures on copper catalysts are also discussed.

Redox Activity of IrIII Complexes with Multidentate Ligands Based on Dipyrido-Annulated N-Heterocyclic Carbenes: Access to High Valent and High Spin State with Carbon Donors.

Synthetic strategies to access high-valent iridium complexes usually require use of π donating ligands bearing electronegative atoms (e. g. amide or oxide) or σ donating electropositive atoms (e. g. boryl or hydride). Besides the η5 -(methyl)cyclopentadienyl derivatives, high-valent η1 carbon-ligated iridium complexes are challenging to synthesize. To meet this challenge, this work reports the oxidation behavior of an all-carbon-ligated anionic bis(CCC-pincer) IrIII complex. Being both σ and π donating, the diaryl dipyrido-annulated N-heterocyclic carbene (dpa-NHC) IrIII complex allowed a stepwise 4e- oxidation sequence. The first 2e- oxidation led to an oxidative coupling of two adjacent aryl groups, resulting in formation of a cationic chiral IrIII complex bearing a CCCC-tetradentate ligand. A further 2e- oxidation allowed isolation of a high-valent tricationic complex with a triplet ground state. These results close a synthetic gap for carbon-ligated iridium complexes and demonstrate the electronic tuning potential of organic π ligands for unusual electronic properties.

Analysis of soot formation in a rapeseed oil-fueled diffusion flame: focusing on the importance of soot in Nara sumi.

Nara sumi is a traditional Japanese craft that has been handed down in Nara since ancient times, and now plays a major role as a regional resource. Soot is considered to be one of the most important materials for its quality. However, the making process has been supported solely by the rule of thumb for craftsmen for many years, and there is very little scientific understanding of that. Therefore, we are focusing on the soot formation process in this study. Soot was collected from different heights in a rapeseed oil-fueled diffusion flame and analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy. As a result, it was confirmed that the formation of the soot shape completes at the bottom of the outside of the flame and that the shape does not change thereafter. It was also confirmed that the oxidation of soot occurs at the bottom of the outside of the flame. These results are expected to contribute to the further scientific understanding of the soot formation process.

Uniform wrapping of copper(I) oxide nanocubes by self-controlled copper-catalyzed azide-alkyne cycloaddition toward selective carbon dioxide electrocatalysis.

Copper(I) oxide nanocubes were wrapped with an extremely uniform organic layer grown by self-controlled, Cu-mediated catalysis. This layer aided in retaining the initial cubic structure of the copper nanocubes during their use as a CO2 reduction electrocatalyst, resulting in high CO2 reduction selectivity by strong suppression of hydrogen evolution because of exclusion of water from the surface.

The [Ag25Cu4H8Br6(CCPh)12(PPh3)12]3+ : Ag13H8 silver hydride core protected by [CuAg3(CCPh)3(PPh3)3]+ motifs.

Copper alkynyl complexes [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ (Ar = Ph, p-C6H4Me), in which three Ag(PPh3) units are bound among three C[triple bond, length as m-dash]CAr arms of trigonal-planar [Cu(C[triple bond, length as m-dash]CAr)3]2-, were selected as a protecting unit to cover the metal core of an atomically precise core-shell-type cluster. First, the formation of the protecting unit through the reaction of Cu(NCMe)4(PF6) with Ag(C[triple bond, length as m-dash]CAr) and PPh3 in a 1 : 3 : 3 ratio was confirmed. The reaction gave dimeric [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]22+, in which the two planar [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ units were stacked. Next, core-shell-type clusters were synthesized by adding NaBH4 and Et4NX (X = Cl, Br) to a solution similar to that used to prepare the protecting unit. The trigonal-planar protecting units nicely formed core-shell-type Ag nanoclusters formulated as [Ag13H8X6{CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3}4]3+ (X = Cl, Ar = p-C6H4Me; X = Br, Ar = p-C6H4Me; X = Br, Ar = Ph). Their crystal structures revealed that the four [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ units are linked by six halogen ions to form a tetrahedral cage that accommodates a polyhydride-Ag cluster formulated as Ag13H85+. As a concrete proof of the existence of the polyhydride, deuterated analogs Ag13D85+ were synthesized and subsequently characterized by high-resolution electrospray-ionization mass spectrometry measurements.

Protonation and electrochemical properties of a bisphosphide diiron hexacarbonyl complex bearing amino groups on the phosphide bridge.

A bisphosphide-bridged diiron hexacarbonyl complex 3 with NEt2 groups on the phosphide bridge was synthesized to examine a new proton relay system from the NEt2 group to the bridging hydride between the two iron centers. As a precursor of the bridging moiety, peri-Et2NP-PNEt2-bridged naphthylene 5 was synthesized by the reaction of 1,8-dilithionaphthylene with two equivalents of Cl2PNEt2 followed by reductive P-P bond formation by magnesium. The reaction of the diphosphine ligand 5 with Fe2(CO)9 gave the diiron hexacarbonyl complex 3, in which the P-P bond of the ligand was cleaved to form the bisphosphide-bridge. The molecular structure of 3 indicated that the trigonal plane of the NEt2 group was forced to face the Fe-Fe bond to avoid steric congestion with the naphthylene group linking the two phosphide groups. The NEt2 group could be protonated by p-toluenesulfonic acid. Density functional theory (DFT) calculations confirmed that the proton of the N(H)Et2 group adopted a position close to the bridging hydride. The DFT results for the ferrocene analogue 1, in which the 1,8-naphthylene group of 3 was replaced with the 1,1'-ferrocenylene group, also revealed that the most stable orientation of the protonated NHEt2 group was that in the protonated 3. As a result, electrochemical proton reduction reactions using complexes 1 and 3 proceeded with similar catalytic efficiencies. Unfortunately, the catalytic efficiencies (CEs) of these complexes were much lower than those of the complexes with a proton relay system of the terminal hydrogen, indicating that the reactive properties of the bridging hydride in the present proton relay system cannot exceed those of the terminal hydride.

On-Surface Modification of Copper Cathodes by Copper(I)-Catalyzed Azide Alkyne Cycloaddition and CO2 Reduction in Organic Environments.

In this study, organic structures were introduced onto copper cathodes to induce changes in their electrocatalytic CO2 reduction activity. Poorly soluble organic polymers were distributed onto the copper surface as a thin layer by polymerizing monomeric precursors via a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) activated by anodization of the copper substrate. The resulting structure possesses copper surface atoms that are available to participate in the CO2 reduction reaction-comparable to close-contact organic structures-and stabilize the adsorption of organic layers through the CO2 reduction process. The CO2 reduction performance of the on-surface modified copper cathode exhibited improved CO2 reduction over H2 evolution compared with traditional cast modification systems. Preventing organic moieties from forming densely packed assemblies on the metal surface appears to be important to promote the CO2 reduction process on the copper atoms. The suppression of H2 evolution, a high methane/ethylene ratio, and the influence of stirring demonstrate that the improved CO2 reduction activity is not only a result of the copper atom reorganization accompanied by repeating anodization for modification; the organic layer also apparently plays an important role in proton transfer and CO2 accumulation onto the copper surface.

Novel chloride-centered Ag18 clusters featuring a cuboctahedral Ag12 skeleton.

Two novel chloride-centered Ag18 clusters with the same framework but different supporting phosphines are synthesized by the reaction of PhC[triple bond, length as m-dash]CAg, AgSbF6, PPh3 (or P(p-Tol)3), and NaBH4 in CH2Cl2, followed by the addition of PhC[triple bond, length as m-dash]CH and NEt3. The inner twelve Ag atoms of these two clusters are arranged in a rare cuboctahedral structure, which can be rationalized by considering a ligand effect. Through careful analysis, we find that the central chloride arises from a generally ignored but nonetheless existing reaction between CH2Cl2 and NEt3, which is well recognized as the Menshutkin reaction. This research provides insights into the dependence of the cluster structure on the nature of the ligand and into the cluster formation mechanism of the Menshutkin reaction.

Synthesis and coordination chemistry of (PNEt2)2-bridged [2]ferrocenophanes.

The trivalent phosphorus-bridged [2]ferrocenophane complex 2 having NEt2 groups on the respective phosphorus centers was prepared, and its reactions as a diphosphine ligand were examined for iron and chromium carbonyl complexes. Both the phosphorus centers of 2 coordinated to Fe(CO)4 fragments to form (µ-2)-[Fe(CO)4]2, while the bulkier Cr(CO)5 fragment formed only a monochromium complex [Cr(κ1-2)(CO)5]. Dissociation of CO from [Cr(κ1-2)(CO)5] changed the coordination mode of 2 from κ1 to κ2 to form [Cr(κ2-2)(CO)4] having a three-membered ring. A similar approach for the monoiron complex [Fe(κ1-2)(CO)4] did not afford a κ2 complex but instead an Et2NPC(O)PNEt2-bridged [3]ferrocenophane complex in which a CO fragment was inserted into the P-P bond of 2 and both the phosphorus centers coordinated to Fe(CO)3 as a chelate diphosphine. The reaction of this product with an Fe(CO)4 fragment gave µ-{Fe(C5H4PNEt2)2-κP:κP}-[Fe(CO)3]2 (8), in which one terminal CO and the CO group between the two phosphorus atoms were lost to give an [FeFe]hydrogenase mimic having a bis(phosphido)ferrocene chelate as a bridging unit. The two NEt2 groups of the bridging unit were expected to work as protonation sites. The protonated NEt2 groups contributed to an improvement in the reduction potential of the complex to a less negative area, i.e., -2.3 V for the free 8 to -1.0 V for the diprotonated 8. The catalytic reduction of the proton, however, required a more negative potential of -2.0 V, which is almost comparable to that of the phosphido-bridged [FeFe]hydrogenase model complex having no protonation site.

Selection of two optional covalent bonds by electric stimuli: dual catalytic switching of redox-active copper.

Two types of redox functionality were selected for covalent immobilization on a carbon electrode, using an electric potential as the sole stimulus. A redox-active copper catalyst transformed a terminal alkyne in two ways with and without an oxidation process, to form a triazole or butadiyne.

A single-molecular twin rotor: correlated motion of two pyrimidine rings coordinated to copper.

We describe the two correlated rotational motions of pyrimidine rings in 4,4'-dimethyl-2,2'-bipyrimidine ligated to Cu(i). The two pyrimidine rings delimited by anthryl and phenanthroline groups rotate to afford three isomers. (1)H NMR measurements revealed that the two rotational processes were activated at different temperatures. Cyclic voltammetry gave the kinetic and thermodynamic parameters that provide clear evidence of the correlation between the two rotational steps.

Regulation of the rate of dinucleation of a monocopper(I) complex containing bipyrimidine rotary units by restricted double pyrimidine rotation.

New copper(I) complexes with coordinated 2-(4'-methyl)pyrimidinyl moieties were fabricated, and the isomerism of their pyrimidine ring linkage was investigated. The ligands bis[2-(diphenylphosphino)phenyl] ether (DPEPhos) and 4,4'-dimethyl-2,2'-bipyrimidine (dmbpm) were used to synthesize a heteroleptic copper(I) complex, [Cu(I)(DPEPhos)(dmbpm)]·BF4 (1·BF4), and a dinuclear copper(I) complex, [(Cu(I))2(DPEPhos)2(µ-dmbmp)](BF4)2 [2·(BF4)2]. The X-ray crystallographic structures, UV-vis absorption spectra, and luminescence properties of the complexes were analyzed. The thermodynamic and kinetic aspects of the isomerism of 1·BF4 were examined by variable-temperature NMR. Double pyrimidine ring rotation was found to be restricted sterically by the bulky DPEPhos ligands. This limited the number of the possible isomers: 1·BF4 showed only isomers with either one (io isomer) or both (oo isomer) of the two methyl groups positioned away from the copper center, while dinuclear 2·(BF4)2 was only found as a symmetric (io-io) isomer, with each of the two methyl groups positioned toward different copper centers. The addition of [Cu(MeCN)2(DPEPhos)] (3·BF4) allowed both isomers of 1·BF4 to form 2·(BF4)2, although at different rates and via different pathways, which were analyzed using time-dependent UV-vis spectroscopy. The io isomer dinucleated more quickly than the oo isomer owing to it being able to form 2·(BF4)2 (i) without bond dissociation and (ii) without a sterically congested ii configuration around the copper center. In contrast, oo-1·BF4 required (i) recombination of the bipyrimidine coordination bonds or (ii) formation of a product with higher thermodynamic energy, unsymmetric (ii-oo) 2·(BF4)2. These findings are interpreted as demonstrating a novel kinetic property: a conversion rate determined by pyrimidine ring inversion.

Structural modification on copper(I)-pyridylpyrimidine complexes for modulation of rotational dynamics, redox properties, and phototriggered isomerization.

The redox properties of copper pyridylpyrimidine complexes, which undergo linkage isomerism based on pyrimidine ring rotation, were compared under different coordination environments. A newly synthesized compound, [Cu(Mepypm)(L(Mes))]BF4 (1·BF4, Mepypm = 4-methyl-2-(2'-pyridyl)pyrimidine, L(Mes) = 2,9-dimesityl-1,10-phenanthroline) was compared with previously reported complexes of [Cu(MepmMepy)(L(Mes))]BF4 (2·BF4, MepmMepy = 4-methyl-2-(6'-methyl-2'-pyridyl)pyrimidine), Cu(Mepypm)(DPEphos)]BF4 (3·BF4, DPEphos = bis[2-(diphenylphosphino)phenyl]ether), [Cu(Mepypm)(L(Anth))]BF4 (4·BF4, L(Anth) = 2,9-bis(9-anthryl)-1,10-phenanthroline), and [Cu(Mepypm)(L(Macro))]BF4 (5·BF4). Isomer ratios, isomerization dynamics, redox properties, and photoelectron conversion functions varied with the coordination structure. Methyl substituents on the 6-position of the pyridine moiety increased steric repulsion and contributed to quicker rotation, enhanced photoluminescence, and increased photodriven rotational isomerization.

Stimuli-responsive pyrimidine ring rotation in copper complexes for switching their physical properties.

This paper summarizes the results of our recent studies on the development of an artificial molecular rotor system that exhibits a change in redox potential and photoluminescence in response to external stimuli such as heat and photons. The molecular rotor is made of copper complexes bearing two bidentate ligands; the rotor is described here as [Cu(Rpmpy)(L(x))](+), where Rpmpy and L(x) are a 4-methyl-2-(2'-pyridyl)pyrimidine derivative and a bidendate ligand with bulky moieties, x, respectively, and the pyrimidine ring can rotate beside the copper centre while maintaining the pyridine-copper connection. The simplicity of the system enabled us to design the rotating motion more accurately. We expected that placing a wall in the rotational trajectory in the L(x) moiety would decrease the rate of the rotational dynamics. This slow rate of rotation was a key factor in achieving an external-stimuli-induced switching from thr equilibrium to metastable states. This switching was based on four stable isomers derived from the rotation and oxidation states, the behaviours of which were characterized for isolated copper(I) complexes using spectroscopic and electrochemical measurements at several temperatures. The steric shifts arising from the ring rotation were exploited not only to exhibit well-established oxidation-triggered motion but also to modulate the rest potential of the electrode, to manipulate the intramolecular electron transfer, to develop a redox potential switch based on photo-driven rotation, and to demonstrate the dual-luminescence behaviour.

Solvated-ion-pairing-sensitive molecular bistability based on copper(I)-coordinated pyrimidine ring rotation.

We describe herein the effect of solvated ion pairing on the molecular motion of a pyrimidine ring coordinated on a copper center. We synthesized a series of heteroleptic copper(I) complex salts bearing an unsymmetrically substituted pyridylpyrimidine and a bulky diphosphine. Two rotational isomers of the complexes were found to coexist and interconvert in solution via intramolecular ligating atom exchange of the pyrimidine ring, where the notation of the inner (i-) and outer (o-) isomers describes the orientation of the pyrimidine ring relative to the copper center. The stability of the pyrimidine orientation was solvent- and counterion-sensitive in both 2·BF(4) {2(+) = [Cu(Mepypm)(dppp)](+), where Mepypm = 4-methyl-2-(2'-pyridyl)pyrimidine and dppp = 1,3-bis(diphenylphosphino)propane} and previously reported 1·BF(4), which possesses a bulky diphosphine ligand (1(+) = [Cu(Mepypm)(DPEphos)](+), where DPEphos = bis[2-(diphenylphosphino)phenyl] ether). Two rotational isomers of 2(+) were separately obtained as single crystals, and the structure of each isomer was examined in detail. Both the enthalpy and entropy values for the rotation of 2·BF(4) in CDCl(3) (ΔH = 6 kJ mol(-1); ΔS = 25 J K(-1) mol(-1)) were more positive than that tested under other conditions, such as in more polar solvents CD(2)Cl(2), acetone-d(6), and CD(3)CN. The reduced contact of the anion to the cation in a polar solvent seems to contribute to the enthalpy, entropy, and Gibbs free energy for rotational isomerization. This speculation based on solvated ion pairing was further confirmed by considering the rotational behavior of 2(+) with a bulky counterion, such as B(C(6)F(5))(4)(-). The findings are valuable for the design of molecular mechanical units that can be readily tuned via weak electrostatic interactions.

Ferrocene-dithiolene hybrids: control of strong donor-acceptor electronic communication to reverse the charge transfer direction.

We prepared a novel class of ferrocene-dithiolene hybrid molecules, FcS4dt(Me)2 and FcS4dt[Pt((t)Bu2bpy)] (where FcS4dt indicates 2-(1,3-dithia[3]ferrocenophane-2-ylidene)-1,3-dithiole-4,5-dithiolate and (t)Bu2bpy indicates 4,4'-di-tert-butyl-2,2'-bipyridine), in which the ferrocene moiety was bound to the planar conjugated dithiolene skeleton via two sulfur atoms such that the cyclopentadienyl rings were perpendicular to the dithiolene backbone. The physical properties and electronic structures of the complexes and their oxidized species [FcS4dt(Me)2](•+) and [FcS4dt[Pt((t)Bu2bpy)]](•+) were investigated by means of single-crystal X-ray diffraction (XRD) analysis, cyclic voltammetry, electron paramagnetic resonance (EPR), and UV-vis near infrared (UV-vis-NIR) spectroscopy. The electron density distributions of the highest occupied molecular orbitals (HOMOs) of FcS4dt(Me)2 and FcS4dt[Pt((t)Bu2bpy)] differed remarkably in that the HOMO of the former was ferrocene-based whereas that of the latter was dithiolene-based. The differences in the HOMO distributions originated from the energy level of the dithiolene-based π-orbital in each of the complexes, which was controlled by changing R in FcS4dt(R)2 (R = Me for FcS4dt(Me)2; 2R = Pt((t)Bu2bpy) for FcS4dt[Pt((t)Bu2bpy)]). We succeeded in analyzing the crystal structure of [FcS4dt[Pt((t)Bu2bpy)]](F4TCNQ)·C6H14·CH2Cl2 (where F4TCNQ indicates 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), which provided a rare example of the crystal structure of a [Pt(diimine)(dithiolate)](•+) ion-based complex. A comparison of the bond lengths in FcS4dt[Pt((t)Bu2bpy)] and [FcS4dt[Pt((t)Bu2bpy)]](•+) suggested that the latter complex displayed a conjugated dithiolene-based π-radical character. These considerations agreed well with the electronic structures calculated using density functional theory (DFT) and time-dependent(TD)-DFT methods. Significant electronic communication between the ferrocene and dithiolene moieties was detected for both [FcS4dt(Me)2](•+) and [FcS4dt[Pt((t)Bu2bpy)]](•+) in the appearance of an intramolecular charge transfer band, which was hardly observed for previously reported ferrocene-dithiolene hybrid molecules. The charge transfer direction was reversed between the two cations. The electron coupling parameter HAB and the potential energy curves of the oxidized complexes were estimated based on the classical two-state Marcus-Hush theory. These results suggest that FcS4dt-based metalladithiolenes can exhibit controllable electronic structures expressed as double-minimum potential energy curves.

Reversible copper(II)/(I) electrochemical potential switching driven by visible light-induced coordinated ring rotation.

We here describe the first metal complex system in which electronic signals can be repeatedly extracted by converting bistable states related to an intramolecular ligand rotational motion, which is fueled by visible light. The molecular structure for relating an electron transfer and a motion consists of a copper center and a coordinated unsymmetrically substituted pyrimidine derivative, whose rotational isomerization causes an electrochemical potential shift. To harness light energy effectively through metal-to-ligand charge transfer (MLCT) excitation, we prepared a simple copper(I) complex coordinated by a 4-methyl-2-(6'-methyl-2'-pyridyl)pyrimidine and a bulky diimine. The thermodynamic and kinetic parameters of redox and rotational reactions were analyzed by cyclic voltammograms at variable temperatures, by considering four stable isomers related to copper(II)/(I) states and rotational isomeric states. The key feature of this compound is that the rotation is frozen in the copper(I) state (rate constant for the rotation, k(Ii→o) = 10(-4) s(-1)) but is active in the copper(II) state (k(IIi→o) = 10(-1) s(-1)) at 203 K. The compound makes a bypass route to the isomeric metastable copper(I) state, via a tentative copper(II) state formed by photoelectron transfer (PET) in the presence of a redox mediator, decamethylferrocenium ion (DMFc(+)), or upon a partial oxidation of the complex. Light- and heat-driven rotation in the copper(I) state with a potential shift (ΔE°' = 0.14 V) was analyzed by electrochemical measurements of the complex in the solution state. The rotor could be reset to the initial state by heating, thereby completing the cycle and enabling repeated operation fueled by light energy. A significant redox potential shift associated with the copper(II)/(I) transition accompanied the rotation, thereby providing a new type of molecular signaling system.

Solid-state ligand-driven light-induced spin change at ambient temperatures in bis(dipyrazolylstyrylpyridine)iron(II) complexes.

We previously reported that an Fe(II) complex ligated by two (Z)-2,6-di(1H-pyrazol-1-yl)-4-styrylpyridine ligands (Z-H) presented a solid state ligand-driven light-induced spin change (LD-LISC) upon one-way Z-to-E photoisomerization, although modulation of the magnetism was trivial at ambient temperatures (Chem. Commun.2011, 47, 6846). Here, we report the synthesis of new derivatives of Z-H, Z-CN and Z-NO(2), in which electron-withdrawing cyano and nitro substituents are introduced at the 4-position of the styryl group to attain a more profound photomagnetism at ambient temperatures. Z-CN and Z-NO(2) undergo quantitative one-way Z-to-E photochromism upon excitation of the charge transfer band both in acetonitrile and in the solid state, similar to the behavior observed for Z-H. In solution, these substituents stabilized the low-spin (LS) states of Z-CN and Z-NO(2), and the behavior was quantitatively analyzed according to the Evans equation. The photomagnetic properties in the solid state, on the other hand, cannot be explained in terms of the substituent effect alone. Z-CN displayed photomagnetic properties almost identical to those of Z-H. Z-CN preferred the high-spin (HS) state at all temperatures tested, whereas photoirradiated Z-CN yielded a lower χ(M)T at ambient temperatures. The behavior of Z-NO(2) was counterintuitive, and the material displayed surprising photomagnetic properties in the solid state. Z-NO(2) occupied the LS state at low temperatures and underwent thermal spin crossover (SCO) with a T(1/2) of about 270 K. The photoirradiated Z-NO(2) displayed a higher value of χ(M)T and the modulation of χ(M)T exceeded that of Z-H or Z-CN. Z-NO(2)·acetone, in which acetone molecules were incorporated into the crystal lattice, further stabilized the LS state (T(1/2) > 300 K), thereby promoting large modulations of the χ(M)T values (87% at 273 K and 64% at 300 K) upon Z-to-E photoisomerization. Single crystal X-ray structure analysis revealed that structural factors played a vital role in the photomagnetic properties in the solid state. Z-H and Z-CN favored intermolecular π-π stacking among the ligand molecules. The coordination sphere around the Fe(II) nucleus was distorted, which stabilized the HS state. In contrast, Z-NO(2)·acetone was liberated from such intermolecular π-π stacking and coordination distortion, resulting in the stabilization of the LS state.

Benzo[e]pyrene skeleton dipyrylium dication with a strong donor-acceptor-donor interaction, and its two-electron reduced molecule.

The donor-acceptor-donor (D-A-D) conjugated molecules 1,4-bis(diarylaminophenylethynyl)anthraquinone (1,4-Am(2)Aq) and 1,4-bis(ferrocenylethynyl)anthraquinone (1,4-Fc(2)Aq), undergo a double proton cyclization reaction with bis(trifluoromethanesulfone)imide acid (TFSIH) to yield 1,4-bis(diarylaminophenyl or ferrocenyl) dipyrylium salts [1,4-R(2)Pyl(2)](TFSI)(2) (R=Am or Fc) with novel planar pentacyclic structures similar to the aromatic benzo[e]pyrene-type skeleton. [1,4-Am(2)Pyl(2)](TFSI)(2) could be reduced to give the neutral molecule [1,4-Am(2)Pyl(2)](0), which is stable and maintains the benzo[e]pyrene-type skeleton. To the best of our knowledge, this is the first oxygen-atom-containing polycyclic aromatic hydrocarbon with 22 (4n+2) π-electrons. The obtained condensed-ring benzo[e]pyrene-type skeleton compounds show physical and chemical properties that are significantly different from those of [1,5-Am(2)Pyl(2)](TFSI)(2), which has a perylene-type skeleton.