[en] Highlights: • Structures of two new coordination polymers based on ligand generated by insitu acylation reaction were reported. • Ligand was originated from in situ acylation reaction of organic acid with N₂H₄. • Selective detection towards 2,4,6–trinitrophenol (TNP) of two coordination polymers was investigated. • The Mn²⁺ compound shows the better selectivity towards the detection of TNP. 2,4,6-Trinitrophenol (TNP), compared with the other nitro compounds, not only has a strong electron-withdrawing ability, but also has a strong light absorption capacity at a large excitation wavelength. Therefore, the fluorescence material with a large excitation wavelength might be a potential probe for the detection of TNP. Here, by employing the in situ acylation of organic acid with N₂H₄, two acylhydrazinotetracarboxylate-based coordination polymers [Cd₂(HL1)(phen)₂(H₂O)]·4.5H₂O (H₅L1​=​5,5′-(1,4-dioxo-1,2,3,4-tetrahydrophthalazine-6,7-diyl)bis(oxy)diisophthalic acid; phen​=​1,10-phenanthroline) 1 and [Mn₂(HL1)(phen)₂]·7H₂O 2 were obtained. Phen is used to prevent the formation of a dense network and many hydrogen bonds, which might quench any emission of material. As predicted, 1 only possesses a 1-D broad-ribbon structure, whereas 2 just has a 1-D tube-like structure. And both are found to emit the yellow light, corresponding to the charge transfer from benzene ring moiety to acylhydrazine ring moiety. It means that the acylation changes thoroughly the photoluminescence behavior of organic ligand. Based on their good photoluminescence properties, the sensing ability of both towards TNP was investigated. It is turned out that 1 is not an ideal sensor, even though it can also sense TNP. However, 2 can be considered as an excellent sensor for the detection of TNP. The emission of 2 is almost completely quenched by TNP, while only 20% quenching is observed for the potential interfering analyte 4-nitroaniline (4-NA). The related sensing mechanism is discussed in details.

[en] Highlights: • Structure of acylhydrazide-based Zn²⁺ coordination polymer was reported. • Acylhydrazide originated from in situ acylation of organic acid with N₂H₄. • It can selectively sensing 2,4,6-trinitrophenol. • (vi) It can also selectively sensing Cr₂O₇^2-. -- Abstract: By employing the hydrothermal in situ acylation of organic acid with N₂H₄, we constructed a new acylhydrazidate-based Zn²⁺ coordination polymer [Zn₂(apo)₂]·H₂O (H₂(apo) = 4,5-diamino-1,2-dihydropyridazine-3,6-diol) 1. Interestingly, besides the acylation of 2,3-pyrazinedicarboxylic acid (pca) with N₂H₄, the breaking of partial C-(=)N bonds in the pyrazine ring also occurred, creating a new bridging-type acylhydrazide molecule H₂(apo). In 1, the apo^2- molecules exhibit a μ₄ coordination mode, linking the tetrahedral Zn²⁺ centers into a 2-D layer network with a 4⁴ topology. The photoluminescence analysis indicates that the title compound 1 emit the green light with the maximum at 490 nm upon excitation (λ_ex = 380 nm, τ = 12.6 μs). Based on the better photoluminescence behavior of 1, the sensing ability of 1 on nitroaromatic explosives and inorganic anions were investigated. The results suggest that 1 can selectively detect 2,4,6-trinitrophenol (TNP) and Cr₂O₇^2-. This should be associated with the larger light adsorption at 380 nm for TNP and Cr₂O₇^2-. The light adsorption at 380 nm for the other nitroaromatic explosives and inorganic anions is weak.

[en] Highlights: • Four new organically templated iodometallates(I) (M⁺ = Ag⁺, Cu⁺) are reported; • In situ N-alkylation of 1,4-diazabicyclo[2,2,2]octane with phenylmethanol is investigated for the first time; • In situ N-alkylation of 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl with alcohol molecules is investigated for the first time; • Their photoluminescence properties at different temperature are investigated. -- Abstract: By employing the solvothermal in situ N-alkylation of organic bases with alcohol molecules, four new organically templated iodometallates as [L1][Ag₂I₄] (L1²⁺ = 1,1,4,4-tetramethyl-1λ⁴,4λ⁴-piperazinium) 1, [L2]_1.5[AgI₄] (L2²⁺ = 1,4-dibenzyl-1λ⁴,4λ⁴-diazabicyclo[2.2.2]octanium) 2, [L2]_1.5[CuI₄] 3 and [L3][CuI₃] (L3²⁺ = 4,4′-bis(3-methyl-1H-3λ⁴-imidazol-1-yl)-1,1′-biphenylium) 4 were obtained. In 1, the in situ substitution and N-alkylation of 1,4-bis(pyridin-4-ylmethyl)piperazine (L1') with CH₃OH has occurred, producing L1²⁺. Templated by L1²⁺, Ag⁺ and I^- aggregate into a chained iodoargentate, which can be described as a linear arrangement of AgI₄ tedrahedra by sharing the edges. 2 and 3 are isostructural. In 2 and 3, the in situ N-alkylation of 1,4-diazabicyclo[2,2,2]octane (L2') with phenylmethanol has occurred, generating L2²⁺. Templated by L2²⁺, Ag⁺ (or Cu⁺) and I^- aggregate into a mononuclear iodometallate with a tetrahedral structure. In 4, the in situ N-alkylation of 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl (L3') with CH₃OH has occurred, creating L3²⁺. Templating by L3²⁺, Cu⁺ and I^- aggregate into a mononuclear iodocuprate(I) with a planar trigonal structure. The photoluminescence analysis reveals that (i) at the room temperature, only 1 emits light (λ_em = 550 nm); (ii) at the low temperature, 4 is found to possess the photoluminescence property (λ_em = 546 nm at 77 K) with a ms-grade lifetime (τ = 4.915 ms).

[en] Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N′-donor ligands yielded three new coordination polymers as [Cu_4(fph)_2(bpe)_3(H_2O)_2]·2H_2O (fph=4,4′-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co_2(fph)(bpa)_2(H_2O)_2]·3H_2O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H_2O)(H_2oph)(bpa)] (oph=4,4′-oxydiphthalate) 3. X-ray single-crystal diffraction analysis revealed that the title three compounds all possess the three-dimensional (3-D) network structures. For compound 1, the fph molecules first link the Cu"2"+ ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. For compound 2, the fph molecules still serve as the first connectors, linking the Co"2"+ ions into a one-dimensional (1-D) tube-like chain. Then the bpa molecules propagate the chains into a 3-D (4,4,4)-connected network. In the formation of the 3-D network of compound 3, the oph molecule does not play a role. The bpa molecules as well as the water molecules act as a mixed bridge. Only a kind of 4-connected metal node is observed in compound 3. The magnetic properties of compounds 1–3 were investigated and all exhibit the predominant antiferromegnetic magnetic behaviors. - Graphical abstract: Structures of three semi-rigid V-shape tetracarboxylate-based coordination polymers were reported, and their magnetic properties were investigated. - Highlights: • Structures of three tetracarboxylate-based coordination polymers were reported. • Role of organic bases in metal–tetracarboxylate compounds was discussed. • Characters of V-shape and semi-rigidity for tetracarboxylate play a key role in crystal growth. • Their magnetic properties were investigated

[en] Under the hydrothermal conditions, the reactions between CuI, KI and bp/bpp (bp=4,4′-bipiperidine, bpp=1,3-bis(4-piperidyl)propane) in an acidic alcohol solution produced three new organically templated iodocuprates(I) as [H₂bp]₂[Cu₂I₆] 1, [tmbp][Cu₂I₄] 2 and [tmbpp] 2 [Cu₄I₈]·2H₂O 3 (tmbp²⁺=N,N,N′,N′-tetramethyl-4,4′-bipiperidinium; tmbpp²⁺=N,N,N′,N′-tetramethyl-1,3-bis(4-piperidyl)propane dication). X-ray analysis revealed that (i) tmbp²⁺ and tmbpp²⁺ in compounds 2 and 3 originated from the complete N-alklation of bp/bpp with CH₃OH; (ii) templated by H₂bp²⁺, the inorganic anion [Cu₂I₆]²⁻ of 1 possesses a dinuclear structure, whereas templated by tmbp²⁺, the inorganic anion [Cu₂I₄]²⁻ of 2 exhibits a one-dimensional (1D) chain structure; (iii) templated by tmbpp²⁺, the inorganic anion [Cu₄I₈]⁴⁻ of 3 shows a cubane-like structure modified by four terminal I⁻ ions. The photoluminescence analysis indicates that compounds 1 and 2 emit blue light, while compound 3 emits green light. - Graphical abstract: By employing hydrothermal in situ N-alkylation of bp/bpp with CH₃OH, three new organically templated iodocuprates(I) were obtained. Display Omitted - Highlights: • Three new organically templated iodocuprates(I) were reported. • Cations tmbp²⁺ and tmbpp²⁺ originated from in situ alkylation of bp/bpp with CH₃OH. • H⁺ and I⁻ play a key role in alkylation of bp/bpp with CH₃OH. • Photoluminescence emission for iodocuprates(I) is related to Cu···Cu interaction

[en] The hydrothermal self-assemblies of Pb²⁺/Cd²⁺ salt, 4,5-dichlorophthalic acid (dcpha), N₂H₄.H₂O together with 1,10-phenanthroline.H₂O (phen) or 2,2'-bipyridine (bpy) generated two new monoacylhydrazidate-bridged 1-D chained coordination polymers [Pb₂(DCPTH)₄(phen)₂] 1 and [Cd₃(DCPTH)₂(dcph)₂(bpy)₂] 2 (DCPTH=4,5-dichlorophthalhydrazidate, dcph=4,5-dichlorophthalate). The monoacylhydrazidate ligand DCPTH originated from the hydrothermal in situ acylation reaction between dcpha and N₂H₄.H₂O. In compound 1, two types of coordination modes for DCPTH are found, which link alternately the Pb(II) centers into a 1-D chain structure of compound 1 with ancillary phen molecules. In compound 2, DCPTH and dcph as the mixed bridges extend the Cd(II) centers into a 1-D chain structure of compound 2 with auxiliary bpy molecules. DCPTH in compound 2 shows a different coordination mode from those observed in compound 1. -- Graphical abstract: By applying the in situ acylation reaction between 4,5-diclorophthalic acid and N₂H₄.H₂O, two 4,5-dichlorophthalhydrazidate-bridged chained compounds [Pb₂(DCPTH)₄(phen)₂] and [Cd₃(DCPTH)₂(dcph)₂(bpy)₂] (4,5-dichlorophthalhydrazidate=DCPTH, and dcph=4,5-dichlorophthalate) were hydrothermally synthesized. Display Omitted Research highlights: → In this article, we first reported the preparations and structural characterization of two examples of 4,5-dichlorophthalhydrazidate-bridged chained coordination polymers [Pb₂(DCPTH)₄(phen)₂] 1 and [Cd₃(DCPTH)₂(dcph)₂(bpy)₂] 2. 4,5-dichlorophthalhydrazidate derived from the hydrothermal in situ acylation reactions between 4,5-dichlorophthalic acid and N₂H₄.H₂O. → In this article, a simple method to judge whether the polycarboxylic acid precursors have acylated into the acylhydrazidate ligands is introduced. → In this article, DFT calculations were carried out on the excited electronic states of the compounds, the fluorescence emission properties of the compounds have been better understood. → this article, by the structural characterization of the obtained monoacylhydrazidate-containing compounds, the character of the monoacylhydrazidate ligands has been further understood.