Solvent Molecule Controlled Zinc(II) Metal‐Organic Frameworks with Different Topology

Two zinc(II) coordination polymers, namely [Zn₂(bptc)(DMF)₂(H₂O)]_n ( 1 ) and [Zn(bptc)_0.5(DMA)]_n ( 2 ) (H₄bptc = biphenyl‐3,3′,5,5′‐tetracarboxylic acid, DMF = N,N′‐dimethylformamide, DMA = N,N′‐dimethylacetamide), were obtained under solvothermal conditions by varying the reaction solvents. Single crystal X‐ray diffraction analyses revealed that compound 1 features a 3D PtS type framework based on dinuclear [Zn₂O(COO)₂] subunits and compound 2 features a 3D lvt type framework based on paddle‐wheel shaped [Zn₂(COO)₄] subunits. Moreover, the luminescent and thermal stabilities of these two compounds were investigated.     

An Effective Method to Construct Cluster‐based Frameworks with Multifarious Structures,Luminescence, and Sorption Properties

An effective method was developed for the synthesis of three cluster‐based frameworks with multifarious secondary building units (SBUs) and various structures, which were formulated as [Me₂NH₂]₂[Zn₁₀(BTC)₆(μ₃‐O)(μ₄‐O)(H₂O)₅] · 3DMA · 9H₂O ( FJI ‐ 3 ), [Me₂NH₂]₂[Zn₉(μ₃‐OH)₂(BTC)₆(H₂O)₃] · 5DMA · 6H₂O ( FJI ‐ 4 ) and [Me₂NH₂][Zn₃(μ₃‐OH)(BTC)₂DMF] · H₂O ( FJI ‐ 5 ) (H₃BTC = 1,3,5‐benzenetricarboxylic acid, DMA = N,N′‐dimethyl acetamide and DMF = N,N′‐dimethyl formamide), respectively. X‐ray structural analysis reveals that FJI ‐ 3 displays 3D highly porous metal‐organic framework with four kinds of microporous cages constructed by two paddle‐wheel Zn₂(CO₂)₄, trimeric Zn₃O(CO₂)₆, and tetrameric Zn₄O(CO₂)₆ SBUs. FJI ‐ 4 exhibits 3D microporous MOFs with a dodecahedral cavities built by paddle‐wheel Zn₂(CO₂)₄ and trimeric Zn₃O(CO₂)₆. FJI ‐ 5 shows 3D microporous MOFs with an 1D channel assembled by the Zn₃O(CO₂)₆ SBUs. In addition, the fluorescence and sorption properties in these cluster‐based frameworks were also investigated. Furthermore, the method employed in this work may provide an useful approach to the design and synthesis of novel cluster‐based frameworks.     

Guest‐Triggered Supramolecular Isomerism in a Pillared‐Layer Structure with Unusual Isomers of Paddle‐Wheel Secondary Building Units by Reversible Single‐Crystal‐to‐Single‐Crystal Transformation

Solvothermal reaction of Zn(NO₃)₂ ? 4 H₂O, 1,4‐bis[2‐(4‐pyridyl)ethenyl]benzene (bpeb) and 4,4′‐oxybisbenzoic acid (H₂obc) in the presence of dimethylacetamide (DMA) as one of the solvents yielded a threefold interpenetrated pillared‐layer porous coordination polymer with pcu topology, [Zn₂(bpeb)(obc)₂] ? 5 H₂O ( 1 ), which comprised an unusual isomer of the well‐known paddle‐wheel building block and the trans–trans–trans isomer of the bpeb pillar ligand. When dimethylformamide (DMF) was used instead of DMA, a supramolecular isomer [Zn₂(bpeb)(obc)₂] ? 2 DMF ? H₂O ( 2 ), with the trans–cis–trans isomer of the bpeb ligand with a slightly different variation of the paddle‐wheel repeating unit, was isolated. In MeOH, single crystals of 2 were transformed by solvent exchange in a single‐crystal‐to‐single‐crystal (SCSC) manner to yield [Zn₂(bpeb)(obc)₂] ? 2 H₂O ( 3 ), which is a polymorph of 1 . SCSC conversion of 3 to 2 was achieved by soaking 3 in DMF. Compounds 1 and 2 as well as 2 and 3 are supramolecular isomers.     

Sorption Behavior and Magnetic Properties of A Heterometallic Organic Framework with Octahedral Cages and One‐Dimensional Channels

The Zn^II‐Co^II organic framework [Me₂NH₂][Zn₂Co(μ₃‐OH)(BTC)₂(H₂O)] · 2H₂O ( FJI‐6 ) (H₃BTC = 1, 3,5‐benzenetricarboxylic acid and DMA = N.N′‐dimethyl acetamide), was synthesized and structurally characterized. FJI‐6 shows a three‐dimensional heterometallic microporous framework with coexisting octahedral cages and one‐dimensional channels assembled by Zn₂Co(μ₃‐OH)(CO₂)₆ secondary building units. In addition, the sorption behavior and magnetic properties of FJI‐6 were investigated.     

Structural Optimization of Interpenetrated Pillared‐Layer Coordination Polymers for Ethylene/Ethane Separation

With the goal of achieving effective ethylene/ethane separation, we evaluated the gas sorption properties of four pillared‐layer‐type porous coordination polymers with double interpenetration, [Zn₂(tp)₂(bpy)]_n ( 1 ), [Zn₂(fm)₂(bpe)]_n ( 2 ), [Zn₂(fm)₂(bpa)]_n ( 3 ), and [Zn₂(fm)₂(bpy)]_n ( 4 ) (tp=terephthalate, bpy=4,4′‐bipyridyl, fm=fumarate, bpe=1,2‐di(4‐pyridyl)ethylene and bpa=1,2‐di(4‐pyridyl)ethane). It was found that 4 , which contains the narrowest pores of all of these compounds, exhibited ethylene‐selective sorption profiles. The ethylene selectivity of 4 was estimated to be 4.6 at 298 K based on breakthrough experiments using ethylene/ethane gas mixtures. In addition, 4 exhibited a good regeneration ability compared with a conventional porous material.     

A Zeolite‐Like Zinc Phosphonocarboxylate Framework and Its Transformation into Two‐ and Three‐Dimensional Structures

Three zinc phosphonocarboxylates, Zn₂(pbc)₂?Hdma?H₃O?2H₂O ( 1 ), Zn(pbc)?Hdma ( 2 ), and Zn_4.5(pbc)₃(OH)(H₂O)_0.5?Hdma ( 3 ) (H₃pbc=4‐phosphonobenzoic acid, dma=dimethylamine) were synthesized by the mixed solvothermal reaction of Zn(Ac)₂?2H₂O and 4‐phosphonobenzoic acid in N,N‐dimethylformamide (DMF) and water. The zigzag and ladderlike chains completely constructed by triply fused 4‐membered rings (denoted SBU‐1) are linked by the organic moieties to form the 3D zeolite‐like structure 1 and the layered structure 2 , respectively. As for structure 3 , a new second building unit (SBU‐2) formed by the inset of the [Zn₃O₁₂] trimer into the 4‐membered ring as well as SBU‐1 is observed. The connections between the two types of SBUs lead to a “zinc phosphate” layer, which is linked by the organic groups to generate a 3D pillar‐layered structure. Both solution‐mediated and solid‐state transformations of 1 to 2 and 3 were observed. A possible mechanism for the transformation is proposed. Gas sorption studies show that 1 has accessible pores for methanol and water and exhibits size selectivity for alcohols.     

A Systematic Study of Fluorescence‐Based Detection of Nitroexplosives and Other Aromatics in the Vapor Phase by Microporous Metal–Organic Frameworks

A systematic study is conducted on four microporous metal–organic framework compounds built on similar ligands but different structures, namely [Zn₃(bpdc)₃(bpy)] ? 4 DMF ? H₂O ( 1 ), [Zn₃(bpdc)₃(2,2′dmbpy)] ? 4 DMF ? H₂O ( 2 ), [Zn₂(bpdc)₂(bpe)] ? 2 DMF ( 3 ), and [Zn(bpdc)(bpe)] ? DMF ( 4 ) (bpdc=4,4′‐biphenyldicarboxylate; bpy=4,4′‐bipyridine; 2,2′dmbpy=2,2′‐dimethyl‐4,4′bipyridine; bpe=1,2‐bis(4‐pyridyl)ethane; DMF=N,N′‐dimethylformamide) to investigate their photoluminescence properties and sensing/detection behavior upon exposure to vapors of various aromatic molecules (analytes) including nitroaromatic explosives. The results show that all four compounds are capable of detecting these molecules in the vapor phase through fluorescence quenching or enhancement. Both electrochemical measurements and theoretical calculations are performed to analyze the analyte–MOF interactions, to explain the difference in signal response by different analytes, and to understand the mechanism of fluorescence quenching or enhancement observed in these systems. Interestingly, compound 3 also shows an emission frequency shift when exposed to benzene (BZ), chlorobenzene (ClBZ), and toluene (TO), which provides an additional variable for the identification of different analytes in the same category.     

X-ray diffraction study of Al-Si melts

New layered metal-organic coordination polymers [Zn₃(bpdc)₃(DMA)₂]·3DMA (1) (H₂bpdc = 4,4′-biphenyldicaboxylic acid, DMA = N,N′-dimethylacetamide) and [Zn₃(bdc)₃(im)₂]·1.5H₂O (2) (H₂bdc = terephtalic acid, im = imidazole) are synthesized and characterized by X-ray crystallography.     

A novel threefold‐interpenetrating primitive cubic network based on a dinuclear Zn2 node

In the mixed‐ligand metal–organic polymeric compound poly[[μ₂‐1,4‐bis(imidazol‐1‐yl)benzene](μ₂‐terephthalato)dizinc(II)], [Zn₂(C₈H₄O₄)₂(C₁₂H₁₀N₄)]_n or [Zn₂(bdc)₂(bib)]_n [H₂bdc is terephthalic acid and bib is 1,4‐bis(imidazol‐1‐yl)benzene], the asymmetric unit contains one Zn^II ion, with two half bdc anions and one half bib molecule lying around inversion centers. The Zn^II ion is in a slightly distorted tetrahedral environment, coordinated by three carboxylate O atoms from three different bdc anions and by one bib N atom. The crystal structure is constructed from the secondary building unit (SBU) [Zn₂(CO₂)₂N₂O₂], in which the two metal centers are held together by two bdc linkers with bis(syn,syn‐bridging bidentate) bonding modes. The SBU is connected by bdc bridges to form a two‐dimensional grid‐like (4,4)‐layer, which is further pillared by the bib ligand. Topologically, the dinuclear SBU can be considered to be a six‐connected node, and the extended structure exhibits an elongated primitive approximately cubic framework. The three‐dimensional framework possesses a large cavity with dimensions of approximately 10 × 13 × 17 Å in cross‐section. The potential porosity is filled with mutual interpenetration of two identical equivalent frameworks, generating a novel threefold interpenetrating network with an α‐polonium topology [Abrahams, Hoskins, Robson & Slizys (2002). CrystEngComm, 4 , 478–482].     

NMR study of localization and mobility of 1‐phenylethanol enantiomers in homochiral metal‐organic sorbent Zn2(bdc)(S‐lac)(dmf)

Structural features of localization of chiral isomers of 1‐phenylethanol (R‐PhEtOH and S‐PhEtOH) and their mobility activation in homochiral metal‐organic [Zn₂(bdc)(S‐lac)(dmf)] sorbent were studied with ¹H and ¹³C NMR methods. ¹³C NMR chemical shifts do not show obvious advantage of selective interaction of molecule guests. But activation molecular mobility of S‐PhEtOH and R‐PhEtOH clearly indicates that stabilization of [Zn₂(bdc)(S‐lac)(dmf)]·S‐PhEtOH structure is more preferable than stabilization of [Zn₂(bdc)(S‐lac)(dmf)]·R‐PhEtOH structure. Copyright © 2015 John Wiley & Sons, Ltd.     

Auxilary Ligand Directed Zinc(II) Metal‐Organic Frameworks with Different Topological Networks

By altering auxiliary N‐donor ligands, two Zn^II compounds, [Zn₃(HL)₂(4,4′‐bipy)₃]_n ( 1 ) and [Zn₄(L)₂(bpp)]_n ( 2 ) (H₄L = 3‐(2′,4′‐dicarboxylphenoxy)phthalic acid, 4,4′‐bipy = 4,4′‐bipyridine, and bpp = 1,3‐bis(4‐pyridyl)propane), were obtained under hydrothermal conditions. Structural analyses revealed that compound 1 features a trinodal (3,4,4)‐connected 3D topological framework, and compound 2 displays a (3,8)‐connected 3D pillar‐layered framework with a tfz‐d topology. Furthermore, the thermal stabilities and the luminescent properties of compounds 1 and 2 were investigated.     

One‐ and Two‐Dimensional PbII Complexes Constructed from N‐Donor Chelating Ligands with Extended π‐System and Organic Dicarboxylates

Two new coordination polymers [Pb(TIP)(1,3‐bdc)]_n ( 1 ) and [Pb(Dpq)(fum)]_n ( 2 ) (TIP = 2‐(2‐thienyl)imidazo[4,5‐f]1,10‐phenanthroline, Dpq = dipyrido[3,2‐d:2′,3′‐f]quinoxaline, 1,3‐H₂bdc = benzene‐1,3‐dicarboxylic acid, fum = fumaric acid) were synthesized by hydrothermal reactions and were characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. Complex 1 is a one‐dimensional (1D) chain, which is bridged by 1,3‐bdc ligands. This is further extended into a three‐dimensional (3D) supramolecular structure by hydrogen bonding interactions. Compound 2 exhibits a two‐dimensional (2D) network structure, which is further stacked by π–π interactions to form a 3D supramolecular framework. The most important feature of these two complexes is that the N‐donor ligands with an extended π‐system play a crucial role in the formation and stabilization of the final supramolecular frameworks. Moreover, the fluorescence property of complex 1 was also investigated in the solid state at room temperature.     

A three‐dimensional coordination polymer based on the Zn4(μ3‐OH)2 unit: poly[[(μ4‐benzene‐1,4‐dicarboxylato)bis(μ3‐benzene‐1,4‐dicarboxylato)bis(μ3‐hydroxido)bis(1,10‐phenanthroline‐5,6‐dione)tetrazinc] dihydrate]

The title compound, {[Zn₄(C₈H₄O₄)₃(OH)₂(C₁₂H₆N₂O₂)₂]·2H₂O}_n, has been prepared hydrothermally by the reaction of Zn(NO₃)₂·6H₂O with benzene‐1,4‐dicarboxylic acid (H₂bdc) and 1,10‐phenanthroline‐5,6‐dione (pdon) in H₂O. In the crystal structure, a tetranuclear Zn₄(OH)₂ fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN₂O₄] octahedron and a [ZnO₄] tetrahedron bridged by a μ₃‐OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN₂O₄] octahedron. The two crystallographically independent bdc²⁻ ligands are fully deprotonated and adopt μ₃‐κO:κO′:κO′′ and μ₄‐κO:κO′:κO′′:κO′′′ coordination modes, bridging three or four Zn^II cations, respectively, from two Zn₄(OH)₂ units. The Zn₄(OH)₂ fragment connects six neighbouring tetranuclear units through four μ₃‐bdc²⁻ and two μ₄‐bdc²⁻ ligands, forming a three‐dimensional framework with uninodal 6‐connected α‐Po topology, in which the tetranuclear Zn₄(OH)₂ units are considered as 6‐connected nodes and the bdc²⁻ ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn₄(OH)₂ unit and are connected to it through hydrogen‐bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π–π interactions between the pdon and μ₄‐bdc²⁻ ligands.     

Synthesis,Structure, Photoluminescence,and Theoretical ­Calculation of an rtl‐type Zinc(II) Compound with Linear Trinuclear [Zn3(COO)4(μ2‐H2O)2] Subunits

The zinc(II) coordination polymer [Zn₃(BPT)₂(μ₂‐H₂O)₂(H₂O)₂]_n · n(DMA) ( 1 ) (H₃BPT = biphenyl‐3,4′,5‐tricarboxylic acid, DMA = N,N′‐dimethylactamide) was obtained by the solvothermal reaction of H₃BPT with Zn(NO₃)₂ in DMA/H₂O mixed solvent. Single crystal X‐ray analysis reveals that compound 1 has a complicated 3D framework containing linear trinuclear [Zn₃(COO)₄(μ₂‐H₂O)₂] clusters as building subunits, which can be simplified into a (3,6)‐connected rtl topological network with the Schläfli symbol {4.6²}₂{4².6¹⁰.8³}. The calculated results of total and partial density of states (DOS) indicate that the luminescence of 1 mainly originates from intraligand charge transfer.     

Two ZnII‐based MOFs constructed with biphenyl‐2,2′,5,5′‐tetracarboxylic acid and flexible N‐donor ligands: syntheses,structures and properties

Two new Zn²⁺‐based metal–organic frameworks (MOFs) based on biphenyl‐2,2′,5,5′‐tetracarboxylic acid, i.e. H₄(o,m‐bpta), and N‐donor ligands, namely, poly[[(μ₄‐biphenyl‐2,2′,5,5′‐tetracarboxylato)bis{[1,3‐phenylenebis(methylene)]bis(1H‐imidazole)}dizinc(II)] dimethylformamide monosolvate dihydrate], {[Zn₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂]·C₃H₇NO·2H₂O}_n or {[Zn₂(o,m‐bpta)(1,3‐bimb)₂]·C₃H₇NO·2H₂O}_n ( 1 ) {1,3‐bimb = [1,3‐phenylenebis(methylene)]bis(1H‐imidazole)}, and poly[[(μ₄‐biphenyl‐2,2′,5,5′‐tetracarboxylato)bis{[1,4‐phenylenebis(methylene)]bis(1H‐imidazole)}dizinc(II)] monohydrate], {[Zn₂(C₁₆H₆O₈)(C₁₄H₁₄N₄)₂]·H₂O}_n or {[Zn₂(o,m‐bpta)(1,4‐bimb)₂]·H₂O}_n ( 2 ) {1,4‐bimb = [1,4‐phenylenebis(methylene)]bis(1H‐imidazole)}, have been synthesized under solvothermal conditions. The complexes were characterized by IR spectroscopy, elemental analysis, single‐crystal X‐ray diffraction and powder X‐ray diffraction analysis. Structurally, the (o,m‐bpta)^4? ligands are fully deprotonated and combine with Zn²⁺ ions in μ₄‐coordination modes. Complex 1 is a (3,4)‐connected porous network with honeycomb‐like [Zn₂(o,m‐bpta)]_n sheets formed by 4‐connected (o,m‐bpta)^4? ligands. Complex 2 exhibits a (2,4)‐connected network formed by 4‐connected (o,m‐bpta)^4? ligands linking Zn²⁺ ions in left‐handed helical chains. The cis‐configured 1,3‐bimb and 1,4‐bimb ligands bridge Zn²⁺ ions to form multi‐membered [Zn₂(bimb)₂] loops. Optically, the complexes show strong fluorescence and display larger red shifts compared to free H₄(o,m‐bpta). Complex 2 shows ferroelectric properties due to crystallizing in the C_2v polar point group.     

Two Coordination Polymers based on 2‐Ethyl‐1H‐imidazole‐4,5‐dicarboxylic Acid and 1,3‐Bis(4‐pyridyl)propane: Synthesis,Crystal Structures,and Photoluminescent Properties

Two coordination polymers, [Cd(Heidc)(bpp)]_n ( 1 ) and [Zn₃ (eidc)₂(bpp)(H₂O)₂] · 2H₂O}_n ( 2 ) (H₃eidc = 2‐ethyl‐4,5‐imidazole dicarboxylic acid, bpp = 1,3‐bis(4‐pyridyl)propane) were hydrothermally synthesized and characterized by elemental analysis, IR, spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 features a 2D layer formed by C–H ··· π stacking interactions between adjacent chains, whereas compound 2 shows a 3D (8³)₂(8⁵.10)‐tfc framework constructed of the 2D (6,3) layer. The result demonstrates that the central metal atoms play a key role in governing the coordination motifs. Moreover, solid‐state properties such as thermal stabilities and photoluminescence of 1 and 2 were also investigated.     

Two Coordination Polymers Constructed from 5‐(4‐Pyridyl)‐1H‐tetrazole Ligands with Different Organic Carboxylates: Structure and Luminescence Properties

Two coordination polymers (CPs), namely, [Cu(Hptz)₂(Hhba)₂]_n ( 1 ) [Hptz = 5‐(4‐pyridyl)‐1H‐tetrazole, H₂hba = 2‐hydroxybenzoic acid] and [Zn₃(ptz)₂(hpa)₂]_n ( 2 ) (H2hpa = 2‐hydroxy‐2‐phenylacetic acid), were synthesized by solvothermal reactions. Both complexes were characterized by elemental analysis, infrared spectroscopy, powder X‐ray diffraction, thermogravimetric analysis, and single‐crystal X‐ray diffraction analysis. Compound 1 exhibits a 2D (4,4) network, where each layer connects to four adjacent layers to construct a 3D supramolecular framework. Compound 2 has a 3D framework structure composed of 1D SUBs, which are formed by both carboxyl and tetrazole groups. The complexes represent two rare examples of CPs constructed from Hptz and organic carboxyl acid ligands. Complex 2 exhibits intense, red‐shifted emissions in the visible region at room temperature.     

Syntheses,Crystal Structures,and Fluorescence Properties of Two Transition Metal‐Organic Coordination Polymers Based on 4,4′‐Dimethyl‐2,2′‐bipyridine

Two transition metal‐organic coordination polymers, [Mn₂(1,3‐bdc)₂(Me₂bpy)₂] · Me₂bpy ( 1 ) and [Co(4,4′‐oba)(Me₂bpy)] ( 2 ) were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, TG, and single‐crystal X‐ray diffraction [1,3‐H₂bdc = benzene‐1,3‐dicarboxylic acid, H₂oba = 4,4′‐oxybis(benzoic acid) Me₂bpy = 4,4′‐dimethyl‐2,2′‐bipyridine]. Compound 1 crystallizes in the orthorhombic system, space group P2₁2₁2₁, with a = 23.371(5), b = 14.419(3), and c = 14.251(3) Å. Compound 2 crystallizes in the monoclinic system, space group P2₁/c, with a = 7.4863(15), b = 18.272(4), c = 16.953(5) Å, and β = 107.44(3)°. The crystal structure of complex 1 is a wave‐like layer with central Mn²⁺ atoms bridged by 1,3‐bdc ligands, whereas the structure of compound 2 presents a ladder chain of hexacoordinate Co²⁺ atoms, in which the metal atoms are bridged by 4,4′‐oba ligands and decorated by Me₂bpy ligands. The two compounds are further extended into 3D supramolecular structures through π–π stacking interactions. Additionally, the compounds show intense fluorescence in solid state at room temperature.     

Synthesis,Structure and Magnetic Property of a Cobalt(II) Metal‐Organic Framework

The three‐dimensional (3D) porous cobalt(II) metal‐organic framework (MOF), [Co₃(L)₂(DMA)₂(MeOH)₂ · 4(DMA) · 6(MeOH)]_n ( 1 ) [L = fully deprotonated 2,7‐bis(4‐benzoic acid)‐N‐(4‐benzoic acid) carbazole, DMA = N,N‐dimethylacetamide], was synthesized by hydrothermal reaction. Based on X‐ray single‐crystal diffraction, structural analysis indicates that complex 1 crystallizes in the monoclinic C2/c space group. Complex 1 possesses a 3,6‐connected three‐dimensional (3D) topological structure with a point symbol of {4² · 6}₂{4⁴ · 6² · 8⁷ · 10²} when a trinuclear Co^II cluster was regarded as 6‐connected node and the organic ligands could be regarded as 3‐connected linkers between the 6‐connected nodes. The framework structure exhibits a one‐dimension (1D) channel with an accessible void of 4223.0 ų, amounting to 42.8 % of the total unit‐cell volume (9862.0 ų). Moreover, the magnetic properties of complex 1 were studied.     

Urothermal Syntheses of two New Luminescent Zinc(II) Compounds via Dual-ligand Strategy

Urothermal reaction of Zn(NO₃)₂ · 6H₂O, Htrz and NH₂H₂pdc or H₂pdc affords two new compounds, namely [Zn₂(NH₂bdc)(trz)₂]_n · 2n(e-urea) ( 1 ) and [Zn₄(bdc)₂(trz)₄(H₂O)(e-urea)]_n · n(e-urea) ( 2 ) (Htrz = 1,2,4-triazole, NH₂H₂bdc = 2-aminoterephthalic acid, H₂bdc = terephthalic acid, e-urea = 1,3-ethyleneurea). X-ray structural analyses revealed that both compounds 1 and 2 feature e-urea-templated 3D pillar-layer framework with 2D Zn^II-triazole layer and 6-connected pcu topological network. These two compounds not only have high thermal stabilities but also show intense luminescence at room temperature.