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A mild and efficient photocatalytic C–H bond activation strategy has been developed by combining redox-active and Brønsted basic dual sites to offer a concerted pathway for H abstraction through concomitant proton and electron transfer.

A bifunctional photocatalyst combining a redox center and a Lewis acid site has been developed for one-pot tandem oxidation–acetalization, which involves pyridinium-mediated molecular oxygen activation, as well as Lewis-acid promoted acetalization.

An eco-friendly and economical approach for the photocatalytic oxidation of organic inter-mediates by air under mild conditions is highly desirable in green and sustainable chemistry, where the photogeneration of active oxygen species plays a key role in improving conversion efficiency and selectivity. By using pyridinium derivatives as molecular mediators for electron transfer and energy transfer, the simultaneous activation of O2 from air into superoxide radicals and singlet oxygen species can be achieved, and a photoinduced electron transfer catalytic system for the oxidation of alcohols has been developed. Thus, we have successfully simplified the complicated catalytic system into a single molecular catalyst without any additional noble metals and co-catalysts/additives. The current photocatalytic system shows high catalytic efficiency not only for aromatic alcohols but also for aliphatic alcohols that are generally difficult to undergo aerobic oxidation at room temperature under air atmosphere, representing an ideal photocatalytic platform for green and economical organic syntheses.

A pyridinium-based complex with environment-friendly and earth-abundant Zn

A Zn(II)-mediated pyridinium-bearing coordination polymer has been successfully synthesized and structurally characterized. The title compound exhibits rapid photochromic properties due to proper structural arrangement of the electron donor and acceptor for PET reaction. Besides, it also displays luminescence switching under the irradiation of 365 nm light.

Based on 1,3-bis(2-methylbenzimidazole)propane (L1), 1,4-bis(2-methylbenzimidazole)butane (L2) and 1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene (L3) with aromatic carboxylic acids, three cocrystals, [(H2L1)2+·2(H2btrc)1−] (1), [(H2L2)2+·(H2btec)2−·2H2O] (2) and [(H2L3)2+·(H2btec)2−] (3) (H3btrc = 1,2,4-benzenetricarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylic acid) were synthesized in solution and obtained by slow evaporation. All solid products were characterized by elemental analyses, IR spectra, and single-crystal X-ray diffraction. Components of the crystalline phase have also been investigated in terms of Hirshfeld surfaces. The bis(benzimidazole) derivatives interlinked with aromatic carboxylates through intermolecular H-bonding and π–π interactions generate diverse 3D supramolecular networks for 1, 2, and 3. The Hirshfeld surfaces and 2D fingerprint plots of three cocrystals show that 1–3 are stabilized by N–H···O, O–H···O, and π–π intermolecular interactions. The thermal stabilities and photoluminescence properties for cocrystals 1–3 were presented in the solid state.

Herein, a nickel coordination polymer (CP 1), {Ni(1,4-bib)1.5(TPA-Cl2)·H2O}n (1,4-bib = 1,4-bis(1H-imidazol-1-yl)benzene, H2TPA-Cl2 = 2,5-dichloro-terephthalic acid), has been synthesized under solvothermal conditions. The structure of CP 1 is a 3D 3-fold interpenetrating framework with the sqc12 topology. The thermal stability and luminescence properties of CP 1 were investigated. Scanning electron microscopy (SEM) images of this material display that it possesses an irregular block 3D structure. Interestingly, CP 1 can serve as a multifunctional material via its luminescence sensing, electrochemical sensing, and photocatalytic properties. The experimental results indicate that CP 1 is an efficient luminescent sensor for the detection of Fe3+ ions in an aqueous solution. In addition, CP 1 exhibits a sensitive and rapid electrochemical response to nitrite ions in water solution. The photocatalytic activities of CP 1 were evaluated in the degradation of different dye contaminants (MB, RhB, and MO), and the results demonstrate that its photocatalytic efficiency for the degradation of MB is highest (92.1% for MB, 85.7% for RhB, and 86.2% for MO). The effects of different dyes, different powers of UV light, and different amounts of catalyst CP 1 on the photocatalytic efficiency were also explored. Finally, the mechanism of the luminescence quenching effect toward Fe3+ ions, electroreduction of nitrite ions, and photocatalytic degradation of different dyes have been investigated in detail.

The hydrothermal reactions of 1,2,4,5-cyclohexanetetracarboxylic acid (H4L) with CoCl2·2H2O and rigid or semi-rigid bis(imidazole) ligands were able to generate two Co(ii) coordination polymers (CPs), {[Co5(L)2(1,4-bimb)(μ3-OH)2(H2O)8]·2H2O}n (1), {[Co(L)0.5(1,4-bib)]·H2O}n (2) (1,4-bimb = 1,4-bis(imidazol-1-ylmethyl)benzene, 1,4-bib = 1,4-bis(1H-imidazol-1-yl)benzene). CPs 1 and 2 were structurally characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction and single crystal X-ray diffraction. CP 1 features a 3D 3,3,4,4,5-connected framework with an unprecedented {42·8·102·12}{43·6·86}2{43}2{46}2{62·8}2 topology, which represents the first example of CPs with such a topology. CP 2 possesses a three-fold interpenetration 3D framework with mog topology. The distinct structures of the two CPs may result from diverse coordination modes of the (L)4- ligands and different structural characteristics of rigid or semi-rigid N-donor ligands. The thermal stabilities, photoluminescence properties and electrochemical behavior in the solid state for CPs 1 and 2 have been investigated. The photophysical studies indicated that CPs 1 and 2 are potential semiconductive materials. Moreover, both CPs 1 and 2 show high photocatalytic efficiency for the degradation of methylene blue (MB) under UV light irradiation and exhibit good stability and recyclability. A possible photocatalytic mechanism is speculated by introducing t-butyl alcohol (TBA) as a widely used ˙OH scavenger.

Surface modification based on a photo-induced electron transfer (PET) reaction in a pyridinium-decorated MOF material was found to be effective in regulating adsorption capacity. The current system enables the adsorption behavior to be manipulated based on variable affinity toward guest molecules through the redistribution of charge population with the preservation of the original pore structure, which is different from the prevalent approaches depending on photoinduced changes in molecular configurations of the pore backbone.

Photodynamic behavior controlled by the synergy of electron transfer and charge transfer has been characterized in two regioisomeric pyridinium-bearing coordination polymers (Cd-Bip and Cd-Bpy) with the help of a smart charge-distribution-related isoreticular strategy. Because it is relatively weak, the charge-transfer interaction between adjacent 2D networks in Cd-Bip can be easily perturbed by photoinduced electron transfer under irradiation with 365 nm light, and then successfully drives the occurrence of photodynamic behavior. In contrast, lower energy 450 nm light is absorbed to a lesser extent, and can only induce a low degree of electron transfer, which is insufficient to actuate operation of this photodynamic behavior in Cd-Bip.

Three coordination polymers, namely {[Ni(L1)(nip)(H2O)]·2H2O} n (1), [Co(L2)(tbip)] n (2), and {[Co2(L3)2(bptc)]·3H2O} n (3) (L1 = 1,4-bis(5,6-dimethylbenzimidazole)butane, L2 = 1,4-bis(5,6-dimethylbenzimidazole)-2-butylene, L3 = 1,3-bis(5,6-dimethylbenzimidazole)propane, H2nip = 5-nitro-isophthalic acid, H2tbip = 5-tert-butyl-isophthalic acid, H4bptc = biphenyl-3,3′,4,4′-tetracarboxylic acid), have been synthesized under hydrothermal conditions and characterized by physicochemical and spectroscopic methods as well as by single-crystal X-ray diffraction analysis. Complexes 1 and 2 both feature a two-dimensional (4,4) layer with (44 × 62) topology. Complex 3 possesses a uninodal 4-connected 2D htb network. The fluorescence spectra and catalytic properties of the complexes for the degradation of methyl orange by sodium persulfate in a Fenton-like process are reported.

Two Cu(i) cyanide coordination polymers (CPs), namely, [Cu2(L1)(CN)2]n (1) and [Cu2(L2)(CN)2]n (2) (L1 = 4,4'-bis(2-methylbenzimidazol-1-ylmethyl)biphenyl, L2 = 4,4'-bis(5,6-dimethylbenzimidazol-1-ylmethyl)biphenyl) were synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, X-ray powder diffraction and elemental analysis. The cyanide ligands in these CPs are generated in situ from the C-C bond cleavage of acetonitrile under solvothermal conditions, which is environmentally friendly and used conveniently. CP 1 features a three-fold interpenetration 3D framework consisting of Cu10(CN)6(L1)4 rings, which represents the first investigation on introducing bis(benzimidazole) ligands into copper(i) cyanide CPs with ThSi2 topology, while CP 2 exhibits a two-dimensional (6,3) layered structure containing Cu6(CN)4(L2)2 rings. The thermal stabilities, and photoluminescence and electrochemical behavior in the solid state of CPs 1 and 2 have been investigated in detail. Moreover, both CP 1 and CP 2 manifest promising photocatalytic activities (photodegradation efficiency using CP 1 is 90.8% and using CP 2 is 87.2%) for the degradation of methylene blue (MB) under UV light irradiation. A possible photocatalytic mechanism is suggested by introducing t-butyl alcohol (TBA) as a widely used ˙OH scavenger.

Nanostructures of a new Co(II) coordination polymer (CP), [Co(Hbibp)(nbta)] n ( 1 ), (bibp = 4,4′-bis(1-imidazolyl)biphenyl, H 3 nbta = 5-nitro-1,2,3-benzenetricarboxylic acid) was synthesized by a sonochemical method. The nano-sized CP 1 was characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction and scanning electron microscopy (SEM). Structural analysis show that CP 1 exhibits a 1D chain structure with a 3-connected SP 1-periodic net (4,4)(0,2) topology, which can be further extended into a 2D supramolecular layer by the N H⋯O hydrogen bond interactions. The thermal stability for CP 1 as bulk and nanoparticles were investigated. The photoluminescence properties and electrochemical behavior for nano-sized CP 1 have also been explored. Moreover, nano-sized CP 1 shows high photocatalytic activities for the degradation of MB under UV irradiation and the photodegradation process is mainly caused by OH radicals. Effects of the sonication time and ultrasonic power on the morphology and size of nanoparticles were studied.