The bromo‐substituted aromatic dicarboxylic acid 5‐amino‐2,4,6‐tribromoisophthalic acid (H2ATBIP), in the presence of the N‐donor flexible bipyridyl‐type ligands 1,3‐bis(pyridin‐4‐yl)propane (bpp) and N,N′‐bis(pyridin‐4‐ylmethyl)oxalamide (4‐bpme) and ZnII ions, was used as an O‐donor ligand to assemble two novel luminescent metal–organic frameworks (MOFs), namely poly[[(μ‐5‐amino‐2,4,6‐tribromoisophthalato‐κ2O1:O3)[μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′]zinc(II)] dimethylformamide monosolvate], {[Zn(C8H2Br3NO4)(C13H14N2)]·C3H7NO}n, (1), and poly[[(μ‐5‐amino‐2,4,6‐tribromoisophthalato‐κ2O1:O3)diaqua[μ‐N,N′‐bis(pyridin‐4‐ylmethyl)oxalamide‐κ2N:N′]zinc(II)] monohydrate], {[Zn(C8H2Br3NO4)(C14H14N4O2)(H2O)2]·H2O}n, (2), using the solution evaporation method. Both (1) and (2) were characterized by FT–IR spectroscopy, elemental analysis (EA), solid‐state diffuse‐reflectance UV–Vis spectroscopy, and powder and single‐crystal X‐ray diffraction analysis. Complex (1) shows a two‐dimensional (2D) corrugated layer simplified as a 2D (4,4) topological network. The supramolecular interactions (π–π stacking, hydrogen bonding and C—Br…Br halogen bonding) play significant roles in the formation of an extended three‐dimensional (3D) supramolecular network of (1). Complex (2) crystallizes in the chiral space group P212121 and exhibits a novel 3D homochiral framework, showing a diamond‐like topology with Schläfli symbol 66. The homochirality of (2) is further confirmed by the solid‐state circular dichroism (CD) spectrum. The second harmonic generation (SHG) property of (2) was also investigated. The hydrogen and C—Br…Br/O halogen bonding further stabilize the framework of (2). The central ZnII ions in (1) and (2) show tetrahedral and octahedral coordination geometries, respectively. The coordinated and uncoordinated water molecules in (2) could be removed selectively upon heating. Most importantly, (1) and (2) show rapid and highly sensitive sensing for a large pool of nitroaromatic explosives (NAEs).
The bromo-substituted aromatic dicarboxylic acid 5-amino-2,4,6-tribromoisophthalic acid (HATBIP) was used to assemble with Cd ions in the presence of the N-donor flexible bipyridyl ligands 3,3'-(diazene-1,2-diyl)dipyridine (mzpy) and 1,3-bis(pyridin-3-ylmethyl)urea (3bpmu), leading to the formation of two chain coordination polymers by adopting solution methods, namely, catena-poly[[[triaqua(5-amino-2,4,6-tribromoisophthalato-κO)cadmium(II)]-μ-3,3'-(diazene-1,2-diyl)dipyridine-κN:N] dihydrate], {[Cd(CHBrNO)(CHN)(HO)]·2HO} or {[Cd(ATBIP)(mzpy)(HO)]·2HO}, (1), and catena-poly[[[tetraaquacadmium(II)]-μ-1,3-bis(pyridin-3-ylmethyl)urea-κN:N-[diaquabis(5-amino-2,4,6-tribromoisophthalato-κO)cadmium(II)]-μ-1,3-bis(pyridin-3-ylmethyl)urea-κN:N] octahydrate], {[Cd(CHBrNO)(CHNO)(HO)]·4HO} or {[Cd(ATBIP)(3bpmu)(HO)]·4HO}, (2). Both complexes were characterized by FT-IR spectroscopic analysis, thermogravimetric analysis (TGA), solid-state diffuse reflectance UV-Vis spectroscopic analysis, and single-crystal and powder X-ray diffraction analysis (PXRD). The mzpy and 3bpmu ligands bridge the Cd metal centres in (1) and (2) into one-dimensional chains, and the ATBIP ligands show a monodentate coordination to the Cd centres in both coordination polymers. A discrete water tetramer exists in (1). Within the chains of (1) and (2), there are halogen bonds between adjacent ATBIP and mzpy or 3bpmu ligands, as well as hydrogen bonds between the ATBIP ligands and the coordinated water molecules. With the aid of weak interactions, the structures of (1) and (2) are further extended into three-dimensional supramolecular networks. An analysis of the solid-state diffuse reflectance UV-Vis spectra of (1) and (2) indicates that a wide indirect band gap exists in both complexes. Complexes (1) and (2) exhibit irreversible and reversible dehydration-rehydration behaviours, respectively, and the solid-state fluorescence properties of both complexes have been studied.
A novel hydrolytic stable Co II -organic framework, namely poly [[bis(2-amino-4-sulfonatobenzoato-O 1 )tetraaquatris{-1,4-bis[(imidazol-1-yl)methyl]benzene-2 N 3 :N 3 0 }dicobalt(II)] tetrahydrate], {[Co(C 7 H 5 NO 5 S)(C 14 H 14 N 4 ) 1.5 (H 2 O) 2 ]Á-2H 2 O} n , (1), based on multifunctional 2-amino-5-sulfobenzoic acid (H 2 asba) and the auxiliary flexible ligand 1,4-bis[(imidazol-1-yl)methyl]benzene (bix), was prepared using the solution evaporation method. The purity of (1) was confirmed by elemental analysis and powder X-ray diffraction (PXRD) analysis. Complex (1) shows a novel 1D!2D interpenetrating network, which is further extended into a 3D supramolecular framework with channels occupied by the lattice water molecules. The 2-amino-4-sulfonatobenzoate (asba 2À ) ligand adopts a monodentate coordination mode. The bix ligands exhibit gauchegauche (GG) and trans-trans (TT) conformations. A detailed analysis of the solid-state diffuse-reflectance UV-Vis spectrum reveals that an indirect band gap exists in the complex. The band structure, the total density of states (TDOS) and the partial density of states (PDOS) were calculated using the CASTEP program. The calculated band gap (E g ) matches well with the experimental one. The complex exhibits a reversible dehydration-rehydration behaviour. Interestingly, gas sorption experiments demonstrate that the new fully anhydrous compound obtained by activating complex (1) at 400 K shows selective adsorption of CO 2 over N 2 . Complex (1) retains excellent framework stability in a variety of solvents and manifests distinct solvent-dependent fluorescence properties. Moreover, the complex shows multiresponsive fluorescence sensing for some nitroaromatics in aqueous medium.
Multifunctional 2-amino-5-sulfobenzoic acid (Hafsb) can exhibit a variety of roles during the construction of supramolecular coordination polymers. The pendant carboxylic acid, sulfonic acid and amino groups could not only play a role in directing bonding but could also have the potential to act as hydrogen-bond donors and acceptors, resulting in extended high-dimensional supramolecular networks. Two new Cu coordination compounds, namely catena-poly[[[diaquacopper(II)]-μ-1,6-bis(1H-1,2,4-triazol-1-yl)hexane-κN:N] bis(3-amino-4-carboxybenzenesulfonate) dihydrate], {[Cu(CHN)(HO)](CHNOS)·2HO} or {[Cu(bth)(HO)](Hafsb)·2HO}, (1), and bis(μ-2-amino-5-sulfonatobenzoato-κO:O)bis{μ-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-κN:N}bis[aquacopper(II)] trihydrate, [Cu(CHNOS)(CHN)(HO)]·3HO or [Cu(afsb)(obix)(HO)]·3HO, (2), have been obtained through the assembly between Hafsb and the Cu ion in the presence of the flexible N-donor ligands 1,6-bis(1H-1,2,4-triazol-1-yl)hexane (bth) and 1,2-bis[(1H-1,2,4-triazol-1-yl)methyl]benzene (obix), respectively. Compound (1) consists of a cationic coordination polymeric chain and 3-amino-4-carboxybenzenesulfonate (Hafsb) anions. Compound (2) exhibits an asymmetric dinuclear structure. There are hydrogen-bonded networks within the lattices of (1) and (2). Interestingly, both (1) and (2) exhibit reversible dehydration-rehydration behaviour.
The assembly of Cu with the multifunctional ligand 2-amino-4-sulfobenzoic acid (Hasba) in the presence of the auxiliary flexible ligands 1,4-bis(triazol-1-ylmethyl)benzene (bbtz) and 1,4-bis(imidazol-1-ylmethyl)benzene (bix) under ambient conditions resulted in two new supramolecular coordination polymers, namely poly[[(3-amino-4-carboxybenzenesulfonato-κO)aquabis[μ-1,4-bis(triazol-1-ylmethyl)benzene-κN:N]copper(II)] 3-amino-4-carboxybenzenesulfonate tetrahydrate], {[Cu(CHNOS)(CHN)(HO)](CHNOS)·4HO}, (1), and poly[[bis(μ-2-amino-4-sulfonatobenzoato-κO:N,O)tetraaqua[μ-1,4-bis(triazol-1-ylmethyl)benzene-κN:N]dicopper(II)] tetrahydrate], {[Cu(CHNOS)(CHN)(HO)]·4HO}, (2). Single-crystal X-ray structure diffraction analysis of (1) reveals that the bbtz ligand acts as a bridge, linking adjacent Cu ions into a two-dimensional cationic (4,4) topological network, in which the coordinated 3-amino-4-carboxybenzenesulfonate (Hasba) anion uses its sulfonate group to bind with the Cu ion in a monodentate fashion and the carboxylate group remains protonated. The lattice Hasba anion resides in the two-dimensional layer and balances the charge. The carboxylate group of the 2-amino-4-sulfonatobenzoate (asba) ligand in (2) is involved in bidentate coordination, connecting adjacent Cu ions into carboxylate-bridged chains which are further bridged by the auxiliary flexible bix ligand in a trans-gauche (TG) mode, resulting in the formation of a two-dimensional network architecture. The amino group of the asba ligand in (2) also takes part in the coordination with the central Cu ion. The six-coordinated Cu centres in (1) and (2) exhibit distorted octahedral coordination geometries. Extensive hydrogen bonding exists in both (1) and (2). The interlayer hydrogen bonds in both compounds further extend adjacent two-dimensional layers into three-dimensional supramolecular network architectures. Furthermore, a detailed analysis of the solid-state UV-Vis-NIR (NIR is near IR) diffuse reflectance data indicates that (1) and (2) may have potential as wide band gap indirect semiconductor materials. Compounds (1) and (2) show reversible and irreversible dehydration-rehydration behaviours, respectively.
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