An isoselective and visual inclusion host system using charge-transfer complexes of 3,3′-disubstituted-1,1′-bi-2-naphthol and methylviologen

A charge-transfer (CT) complex, composed of rac-3,3′-dibromo-1,1′-bi-2-naphthol as the electron donor and 1,1′-dimethyl-4,4′-bipyridinium dichloride as the electron acceptor, is formed only by the inclusion of specific guest molecules. The color of this inclusion CT complex is sensitive to the component guest molecules.     

Charge-transfer host complex with channel-like cavity using disubstituted-1,1′-bi-2-naphthol and benzylviologen

A novel charge-transfer (CT) host system is developed using CT complexes composed of rac-3,3′-dihydroxy-1,1′-bi-2-naphthol and 1,1′-dibenzyl-4,4′-bipyridinium dichloride. This CT host complex has a 1D channel-like cavity in which guest (MeOH and EtOH) molecules can be discharged and adsorbed. The color and DRS of the CT crystals change according to the presence of guest molecules in the host complex.     

A charge-transfer host system composed of a chiral 1,1′-bi-2-naphthol cluster and benzylviologen

Chiral charge-transfer (CT) complexes composed of a chiral 1,1′-bi-2-naphthol cluster as the electron donor and 1,1′-dibenzyl-4,4′-bipyridinium dichloride as the electron acceptor serve as a host system for molecular recognition. CT complexes that include guest alcohols show different diffuse reflectance spectra (DRS) depending on the included guest.     

Charge-transfer host system composed of 9,10-bis(3,5-dihydroxyphenyl)anthracene and methylviologen

By using 9,10-bis(3,5-dihydroxyphenyl)anthracene as an electron donor and 1,1′-dimethyl-4,4′-bipyri-dinium dichloride as an electron acceptor, a spontaneously resolved charge-transfer (CT) complex is formed. This CT complex can include n-alkyl alcohol molecules as guests, and the DRS of this CT complex change with the type of component guest molecules.     

Guest-Selective Recognition in a Flexible Bipyridinium-Based Framework in a Reversible Crystal-to-Crystal Fashion

A flexible bipyridinium-linker-based porous host framework with electron-accepting pore surface, namely, [Zn₂( L )(pmc)_1.5] ⋅ 12 H₂O ( 1 ; L⋅ Cl₂=1,1′-[1,4-phenylene-bis(methylene)]bis(4,4′-bipyridinium) dichloride, H₄pmc=pyromellitic acid) exhibits recognition of phenol and aromatic amine guests based on adsorbent–adsorbate charge-transfer interactions. Significantly, the resultant guest-encapsulated complexes 1@Guests can all be characterized by single-crystal X-ray diffraction. The host framework undergoes a reversible single crystal-to-single crystal transformation in response to the inclusion of different guests with flexible torsional motions of the hexagonal ring and the trapezoid-shaped bipyridinium groups. Such recognition can be visibly monitored and detected by obvious color changes. The host framework could also be recovered, and this suggested that guest sorption/desorption is reversible and that the host framework could be reused in potential applications. This work may provide an effective way to develop porous materials with special emphasis on applications involving guest recognition.     

A charge-transfer complex of 10,10'-dihydroxy-9,9'-biphenanthryl and methylviologen as a visual inclusion host system

A charge-transfer (CT) complex, composed of 10,10'-dihydroxy-9,9'-biphenanthryl as the electron donor and 1,1'-dimethyl-4,4'-bipyridinium dichloride as the electron acceptor, is formed only by the inclusion of guest molecules. The color of this inclusion CT complex is sensitive to the component guest molecules.     

Interaction between cucurbit[8]uril and viologen derivatives

The interaction between cucurbit[8]uril (Q[8]) and a series of symmetric viologen derivatives having aliphatic substituents of variable length [N,N′-dialkyl-4,4′-bipyridinium dianions; alkyl = CH₃(CH₂) _n –, n = 0 (MV²⁺), 1 (EV²⁺), 2 (PV²⁺), 3 (BV²⁺), 4 (FV²⁺), 5 (HV²⁺) or 6 (SV²⁺); BPY²⁺ = diprotonated 4,4-bipyridine], determined by ¹H NMR and electronic absorption spectroscopy methods, is described. Some different binding models were observed in this work when compared to the interactions between cucurbit[7]uril (Q[7]) and these guests. The experimental results revealed that the binding site of the guests by Q[8] depended strongly on the length of the aliphatic substituents on the 4,4′-bipyridinium nucleus. While a 1:2 complex was observed for Q[8]-BPY²⁺ under acidic conditions, a 1:1 complex was formed for Q[8]-viologen derivatives with chains shorter than four carbon atoms. However, multiple Q[8] molecules could be threaded on the longer-chain FV²⁺, HV²⁺ or SV²⁺ molecules to form 2:1 and even possibly 3:1 complexes.     

A charge‐transfer salt composed of methyl viologen and hexacyanidoferrate(II)

The methyl viologen dication, used under the name Paraquat as an agricultural reagent, is a well‐known electron‐acceptor species that can participate in charge‐transfer (CT) interactions. The determination of the crystal structure of this species is important for accessing the CT interaction and CT‐based properties. The title hydrated salt, bis(1,1′‐dimethyl‐4,4′‐bipyridine‐1,1′‐diium) hexacyanidoferrate(II) octahydrate, (C₁₂H₁₄N₂)₂[Fe(CN)₆]·8H₂O or (MV)₂[Fe(CN)₆]·8H₂O [MV²⁺ is the 1,1′‐dimethyl‐4,4′‐bipyridine‐1,1′‐diium (methyl viologen) dication], crystallizes in the space group P 2₁/c with one MV²⁺ cation, half of an [Fe(CN)₆]⁴⁻ anion and four water molecules in the asymmetric unit. The Fe^II atom of the [Fe(CN)₆]⁴⁻ anion lies on an inversion centre and has an octahedral coordination sphere defined by six cyanide ligands. The MV²⁺ cation is located on a general position and adopts a noncoplanar structure, with a dihedral angle of 40.32 (7)° between the planes of the pyridine rings. In the crystal, layers of electron‐donor [Fe(CN)₆]⁴⁻ anions and layers of electron‐acceptor MV²⁺ cations are formed and are stacked in an alternating manner parallel to the direction of the −2a + c axis, resulting in an alternate layered structure.     

A Chiral Emissive Conjugated Corral for High-Affinity and Highly Enantioselective Recognition in Water

Accurately distinguishing between enantiomeric molecules is a fundamental challenge in the field of chemistry. However, there is still significant room for improvement in both the enantiomeric selectivity (K_R(S)/K_S(R)) and binding strength of most reported macrocyclic chiral receptors to meet the demands of practical application scenarios. Herein, we synthesized a water-soluble conjugated tubular host—namely, corral[4]BINOL—using a chiral 1,1′-bi-2-naphthol (BINOL) derivative as the repeating unit. The conjugated chiral backbone endows corral[4]BINOL with good fluorescent emission (QY=34 % ) and circularly polarized luminescence (|g_lum| up to 1.4×10⁻³) in water. Notably, corral[4]BINOL exhibits high recognition affinity up to 8.6×10¹⁰ M⁻¹ towards achiral guests in water, and manifested excellent enantioselectivity up to 18.7 towards chiral substrates, both of which represent the highest values observed among chiral macrocycles in aqueous solution. The ultrastrong binding strength, outstanding enantioselectivity, and facile accessibility, together with the superior fluorescent and chiroptical properties, endow corral[4]BINOL with great potential for a wide range of applications.     

Photo Responsive Electron and Proton Conductivity within a Hydrogen-Bonded Organic Framework

Rational design of crystalline porous materials with coupled proton-electron transfer has not yet been reported to date. Herein, we report a donor-acceptor (D-A) π-π stacking hydrogen-bonded organic framework (HOF; HOF-FJU-36 ) with zwitterionic 1,1′-bis(3-carboxybenzyl)-4,4′-bipyridinium (H₂L²⁺) as acceptor and 2,7-naphthalene disulfonate (NDS²⁻) as donor to form a two-dimensional (2D) layer. Three water molecules were situated in the channels to connect with acidic species through hydrogen bonding interactions to give a 3D framework. The continuous π-π interactions along the a axis and the smooth H-bonding chain along the b axis provide the electron and proton transfer pathways, respectively. After 405 nm light irradiation, the photogenerated radicals could simultaneously endow HOF-FJU-36 with photoswitchable electron and proton conductivity due to coupled electron-proton transfer. By single-crystal X-ray diffraction (SCXRD) analyses, X-ray photoelectron spectroscopy (XPS), transient absorption spectra and density functional theory (DFT) calculations, the mechanism of the switchable conductivity upon irradiation has been demonstrated.     

Synthesis and crystal structures of 3D supramolecular compounds: [ M (4,4′-bipy)2(H2O)4] · (4,4′-bipy)2 · (3,5-daba)2 · 8H2O ( M =Zn,Mn)

Two new supramolecular compounds [M(4,4′-bipy)₂ (H₂O)₄] ·?(4,4′-bipy)₂ ·?(3,5-daba)₂ ·?8H₂O (M=Zn(1) or Mn(2), 4,4′-bipy =?4,4′-bipyridine, 3,5-daba =?3,5-diaminobenzoic acid anion) were synthesized and characterized by elemental analysis and X-ray crystal diffraction. In [M(4,4′-bipy)₂(H₂O)₄]²⁺, the M(II) is coordinated by two nitrogen atoms from two 4,4′-bipy molecules and four oxygen atoms from four waters to form an octahedral configuration. There exist uncoordinated 4,4′-bipy molecules, 3,5-diaminobenzolate counterions and water guests in the compounds. The 3D structures of the title supramolecular compounds are constructed by rich hydrogen bonds among [M(4,4′-bipy)₂(H₂O)₄]²⁺, uncoordinated 4,4′-bipy molecules, water molecules and 3,5-daba, containing a diverting hexa-member water ring.     

Inclusion of chlorophenols by 4,4′‐(cyclohexane‐1,1‐diyl)diphenol: structures and kinetics of decomposition

The structures of the inclusion compounds 4,4′‐(cyclohexane‐1,1‐diyl)diphenol–3‐chlorophenol (1/1) and 4,4′‐(cyclohexane‐1,1‐diyl)diphenol–4‐chlorophenol (1/1), both C₁₈H₂₀O₂·C₆H₅ClO, are isostructural with respect to the host molecule and are stabilized by extensive host–host, host–guest and guest–host hydrogen bonding. The packing is characterized by layers of host and guest molecules. The kinetics of thermal decomposition follow the R2 contracting‐area model, kt = [1 − (1 − α)^½], and yield activation energies of 105 (8) and 96 (8) kJ mol⁻¹, respectively.     

One-Dimensionally Disordered Chiral Sorting by Racemic Tiling in a Surface-Confined Supramolecular Assembly of Achiral Tectons

The aggregation of (pro)chiral/achiral molecules into crystalline structures at interfaces forms conglomerates, racemates, and solid solutions, comparable to known bulk phases. Scanning tunneling microscopy and Monte Carlo simulations were employed to uncover a distinct racemic phase, expressing 1D disordered chiral sorting through random tiling in surface-confined supramolecularly assembled achiral 4,4′′-diethynyl-1,1′:4′,1′′-terphenyl molecules. The configurational entropy of the 1D disordered racemic tiling phase was verified by analytical modeling, and found to lie between that of a perfectly ordered 2D racemate and a racemic solid solution.     

One‐Dimensionally Disordered Chiral Sorting by Racemic Tiling in a Surface‐Confined Supramolecular Assembly of Achiral Tectons

The aggregation of (pro)chiral/achiral molecules into crystalline structures at interfaces forms conglomerates, racemates, and solid solutions, comparable to known bulk phases. Scanning tunneling microscopy and Monte Carlo simulations were employed to uncover a distinct racemic phase, expressing 1D disordered chiral sorting through random tiling in surface‐confined supramolecularly assembled achiral 4,4′′‐diethynyl‐1,1′:4′,1′′‐terphenyl molecules. The configurational entropy of the 1D disordered racemic tiling phase was verified by analytical modeling, and found to lie between that of a perfectly ordered 2D racemate and a racemic solid solution.     

Electrochromic Detection of Latent Fingermarks on Metal Surface Using 1,1′-Dibenzyl-4,4′-bipyridinium Dichloride

The electrochromic detection of latent fingermarks on polished or unpolished, flat or curved metal surfaces is described using electrochromic material, 1,1’-dibenzyl-4,4’-bipyridinium dichloride. The surface area covered by fingermarks acts as an insulating mask, causing 1,1’-dibenzyl-4,4’-bipyridinium dichloride to change color and produce inversed images of the fingermark. By changing the applied potential, the optical properties of 1,1’-dibenzyl-4,4’-bipyridinium dichloride can be continuously and reversibly adjusted to optimize the visual contrast of fingermarks, so as to realize the detection of latent fingermarks on stainless steel surface. It is demonstrated that the fabricated electrochromic devices can detect the fingermarks on these types of surfaces within twenty seconds at −1.0∼−2.0 V. This work can qualify as a tangible improvement in fingermark detection of the natural fingermarks on the never-cleaned (more than 3 years) and curved surfaces of daily-used container, e. g. cup, and the handle of cleaning tool, mop.     

Cobalt(II) chloride complexes with 1,1′‐dimethyl‐4,4′‐bipyrazole featuring first‐ and second‐sphere coordination of the ligand

In catena‐poly[[dichloridocobalt(II)]‐μ‐(1,1′‐dimethyl‐4,4′‐bipyrazole‐κ²N²:N^2′)], [CoCl₂(C₈H₁₀N₄)]_n, (1), two independent bipyrazole ligands (Me₂bpz) are situated across centres of inversion and in tetraaquabis(1,1′‐dimethyl‐4,4′‐bipyrazole‐κN²)cobalt(II) dichloride–1,1′‐dimethyl‐4,4′‐bipyrazole–water (1/2/2), [Co(C₈H₁₀N₄)₂(H₂O)₄]Cl₂·2C₈H₁₀N₄·2H₂O, (2), the Co²⁺ cation lies on an inversion centre and two noncoordinated Me₂bpz molecules are also situated across centres of inversion. The compounds are the first complexes involving N,N′‐disubstituted 4,4′‐bipyrazole tectons. They reveal a relatively poor coordination ability of the ligand, resulting in a Co–pyrazole coordination ratio of only 1:2. Compound (1) adopts a zigzag chain structure with bitopic Me₂bpz links between tetrahedral Co^II ions. Interchain interactions occur by means of very weak C—H...Cl hydrogen bonding. Complex (2) comprises discrete octahedral trans‐[Co(Me₂bpz)₂(H₂O)₄]²⁺ cations formed by monodentate Me₂bpz ligands. Two equivalents of additional noncoordinated Me₂bpz tectons are important as `second‐sphere ligands' connecting the cations by means of relatively strong O—H...N hydrogen bonding with generation of doubly interpenetrated pcu (α‐Po) frameworks. Noncoordinated chloride anions and solvent water molecules afford hydrogen‐bonded [(Cl⁻)₂(H₂O)₂] rhombs, which establish topological links between the above frameworks, producing a rare eight‐coordinated uninodal net of {4²⁴.5.6³} ( ilc ) topology.     

烷基链长对紫精分子在Cu(100)电极表面吸附结构的影响

用循环伏安法(CV)和原位扫描隧道显微镜(STM)研究了烷基取代的紫精分子在Cu(100)电极上的氧化还原行为及其吸附结构对电极电势的依赖性. 对乙基紫精(DHV)和庚基紫精(DEV)在含有KCl电解质溶液中进行循环伏安曲线的测定, 两者呈现出不同的氧化还原行为. 从STM所得图像观察, 二价庚基紫精在Cl-c(2×2)-Cu(100)电极上呈现出二维有序的点阵组装结构,而二价乙基紫精却未出现任何的吸附结构. 降低电极电势至单电子转移反应发生时, 形成的自由基庚基紫精在电极表面呈现出稳定的条带状组装结构, 而自由基乙基紫精出现的条带组装结构比较密集且不能稳定存在. 继续降低电极电势, 庚基紫精的吸附结构会随之出现明显的变化,而乙基紫精不会有吸附结构改变的响应.     

A three‐dimensional homochiral metal–organic framework constructed from manganese(II) with S‐carboxymethyl‐N‐(p‐tosyl)‐l‐cysteine and 4,4′‐bipyridine

In the chiral polymeric title compound, poly[aqua(4,4′‐bipyridine)[μ₃‐S‐carboxylatomethyl‐N‐(p‐tosyl)‐l ‐cysteinato]manganese(II)], [Mn(C₁₂H₁₃NO₆S₂)(C₁₀H₈N₂)(H₂O)]_n, the Mn^II ion is coordinated in a distorted octahedral geometry by one water molecule, three carboxylate O atoms from three S‐carboxyatomethyl‐N‐(p‐tosyl)‐l ‐cysteinate (Ts‐cmc) ligands and two N atoms from two 4,4′‐bipyridine molecules. Each Ts‐cmc ligand behaves as a chiral μ₃‐linker connecting three Mn^II ions. The two‐dimensional frameworks thus formed are further connected by 4,4′‐bipyridine ligands into a three‐dimensional homochiral metal–organic framework. This is a rare case of a homochiral metal–organic framework with a flexible chiral ligand as linker, and this result demonstrates the important role of noncovalent interactions in stabilizing such assemblies.     

Colored supramolecular charge-transfer host system using 10,10′-dihydroxy-9,9′-biphenanthryl and 2,5-disubstituted-1,4-benzoquinone

A colored charge-transfer (CT) host complex is formed using racemic (rac)-10,10′-dihydroxy-9,9′-biphenanthryl, which has a large and widely π-conjugated phenanthrene ring, as the electron donor and 2,5-disubstituted-1,4-benzoquinone as the electron acceptor. This CT host complex can include aromatic molecules as guests and its color and diffuse reflectance spectra (DRS) change according to the type of guest molecules included. Characteristically, it is possible to tune the color and DRS of the inclusion CT complex by changing the type of the component 2,5-disubstituted-1,4-benzoquinone.     

Bipyridinium Array‐Type Porous Polymer Displaying Hydrogen Storage,Charge‐Transfer‐Type Guest Inclusion,and Tunable Magnetic Properties

A multifunctional pillared‐layer porous coordination polymer, {[Mn₂(Bpybc)(ox)₂] ? 8 H₂O}_n, has been constructed based on a flexible viologen derivative, 1,1′‐bis(4‐carboxybenzyl)‐4,4′‐bipyridinium dichloride (H₂BpybcCl₂), and an oxalate (ox) coligand. Single‐crystal X‐ray analysis reveals that the compound possesses multichannels with dimensions of about 6.1×6.6 Å along the [110] and [?110] directions and 4.2×7.6 Å along [100], and a void space of about 41.4 %. Hydrogen adsorption measurements at 77 K and 1 atm indicate that the compound exhibits a hydrogen uptake of 0.71 wt %. Owing to the incorporation of bipyridinium acceptor units, the compound can selectively accommodate aromatic donors into its nanosized pores based on charge‐transfer interactions in an elastic way, and afford a specific color to different guests. Furthermore, the effect of perturbation exerted by the guest molecules on its magnetic properties has been investigated. The results indicate that the donor inclusion has little effect on its antiferromagnetic behavior, whereas dehydration of the compound decreases the strength of the magnetic exchange couplings and results in a change of the antiferromagnetic transition temperature from 14.7 to 9.8 K.