A three‐dimensional polymeric potassium complex of 5‐sulfonobenzene‐1,2,4‐tricarboxylic acid: poly[μ‐aqua‐aqua‐μ9‐(2,4‐dicarboxy‐5‐sulfonatobenzoato)‐dipotassium(I)]

The asymmetric unit in the structure of the title compound, [K₂(C₉H₄O₉S)(H₂O)₂]_n, consists of two eight‐coordinated K^I cations, one 2,4‐dicarboxy‐5‐sulfonatobenzoate dianion (H₂SBTC²⁻), one bridging water molecule and one terminal coordinated water molecule. One K^I cation is coordinated by three carboxylate O atoms and three sulfonate O atoms from four H₂SBTC²⁻ ligands and by two bridging water molecules. The second K^I cation is coordinated by four sulfonate O atoms and three carboxylate O atoms from five H₂SBTC²⁻ ligands and by one terminal coordinated water molecule. The K^I cations are linked by sulfonate groups to give a one‐dimensional inorganic chain with cage‐like K₄(SO₃)₂ repeat units. These one‐dimensional chains are bridged by one of the carboxylic acid groups of the H₂SBTC²⁻ ligand to form a two‐dimensional layer, and these layers are further linked by the remaining carboxylate groups and the benzene rings of the H₂SBTC²⁻ ligands to generate a three‐dimensional framework. The compound displays a photoluminescent emission at 460 nm upon excitation at 358 nm. In addition, the thermal stability of the title compound has been studied.     

Effect of Medium Acidity and Photostability of 3‐(4‐Dimethylamino‐phenyl)‐1‐(2,5‐dimethyl‐thiophen‐3‐yl)‐propenone (DDTP): A New Green Emitting Laser Dye

On the line of a previous work on the spectral properties of some of heteroaryl chalcone, the effect of medium acidity and photoreactivity of 3‐(4‐dimethylamino‐phenyl)‐1‐(2,5‐dimethyl‐thiophen‐3‐yl)‐propenone (DDTP) has been investigated in dimethylformamide and in chloromethane solvents such as methylenechloride, chloroform and carbon tetrachloride. The dye solution (ca. 5×10⁻⁴ mol·L⁻¹ in DMF) gives a good laser emission in the range 470–560 nm with emission maximum at 515 nm upon pumping by nitrogen laser (λ_ex=337.1 nm). The laser parameters such as gain coefficient (α), emission cross section (δ_e) and half life energy (E_1/2) at maximum laser emission are also determined.     

catena‐Poly[[[diaquazinc]‐bis{μ‐N2,N6‐bis[(pyridin‐3‐yl)methyl]pyridine‐2,6‐dicarboxamide}] dinitrate]

In the title compound, {[Zn(C₁₉H₁₇N₅O₂)₂(H₂O)₂](NO₃)₂}_n, the Zn^II cation is located at an inversion centre within a slightly distorted octahedron, ligated by four N atoms from four N²,N⁶‐bis[(pyridin‐3‐yl)methyl]pyridine‐2,6‐dicarboxamide (L) ligands occupying a plane about the Zn^II atom with the two water O atoms perpendicular to that. In the complex molecule, the bidentate bridging L ligands display helical R and S conformers, and link the Zn^II cations into a one‐dimensional centrosymmetric double‐chain structure containing 32‐membered rings. The nitrate anions reside in these rings and are involved in multiple N—H...O hydrogen‐bond interactions. On excitation at 390 nm, the title compound displays a strong blue emission centred at 449 nm. Investigation of the thermal stability shows that the network structure is stable up to 420 K.     

A new one‐dimensional nickel metal–organic framework: catena‐poly[[[diaquabis(4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoato‐κO)nickel(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′] monohydrate]

The title complex, {[Ni(C₁₅H₁₁N₄O₂S)₂(C₁₀H₈N₂)(H₂O)₂]·H₂O}_n, was synthesized by the reaction of nickel chloride, 4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoic acid (HL) and 4,4′‐bipyridine (bpy) under hydrothermal conditions. The asymmetric unit contains two half Ni^II ions, each located on an inversion centre, two L⁻ ligands, one bpy ligand, two coordinated water molecules and one unligated water molecule. Each Ni^II centre is six‐coordinated by two monodentate carboxylate O atoms from two different L⁻ ligands, two pyridine N atoms from two different bpy ligands and two terminal water molecules, displaying a nearly ideal octahedral geometry. The Ni^II ions are bridged by 4,4′‐bipyridine ligands to afford a linear array, with an Ni...Ni separation of 11.361 (1) Å, which is further decorated by two monodentate L⁻ ligands trans to each other, resulting in a one‐dimensional fishbone‐like chain structure. These one‐dimensional fishbone‐like chains are further linked by O—H...O, O—H...N and C—H...O hydrogen bonds and π–π stacking interactions to form a three‐dimensional supramolecular architecture. The thermal stability of the title complex was investigated via thermogravimetric analysis.     

catena‐Poly[[[diaqua[3‐(pyridin‐4‐yl)benzoato‐κ2O,O′]terbium(III)]‐bis[μ‐3‐(pyridin‐4‐yl)benzoato‐κ2O:O′]] monohydrate]

In the title compound, {[Tb(C₁₂H₈NO₂)₃(H₂O)₂]·H₂O}_n, the Tb^III cation is in an eight‐coordinate environment, ligated by six carboxylate O atoms from five 3‐(pyridin‐4‐yl)benzoate (L) ligands and by two O atoms from water molecules. The cations are bridged by the carboxylate O atoms of the L ligands to form a two‐stranded polymeric chain which is assembled into a three‐dimensional supramolecular network through regular interchain O—H...N hydrogen bonding. On excitation at 320 nm, the title compound displays a series of emissions, which were assigned to the characteristic electronic transitions of Tb^III.     

A two‐dimensional cadmium(II) coordination polymer based on 5‐(pyridin‐4‐yl)isophthalic acid: poly[[tetraaquabis[μ3‐5‐(pyridin‐4‐yl)isophthalato]dicadmium(II)] pentahydrate]

The title Cd^II compound, {[Cd₂(C₁₃H₇NO₄)₂(H₂O)₄]·5H₂O}_n, was synthesized by the hydrothermal reaction of Cd(NO₃)₂·4H₂O and 5‐(pyridin‐4‐yl)isophthalic acid (H₂L). The asymmetric unit contains two crystallographically independent Cd^II cations, two deprotonated L²⁻ ligands, four coordinated water molecules and five isolated water molecules. One of the Cd^II cations adopts a six‐coordinate octahedral coordination geometry involving three O atoms from one bidentate chelating and one monodentate carboxylate group of two different L²⁻ ligands, one N atom of another L²⁻ ligand and two coordinated water molecules. The second Cd^II cation adopts a seven‐coordinate pentagonal–bipyramidal coordination geometry involving four O atoms from two bidentate chelating carboxylate groups of two different L²⁻ ligands, one N atom of another L²⁻ ligand and two coordinated water molecules. Each L²⁻ ligand bridges three Cd^II cations and, likewise, each Cd^II cation connects to three L²⁻ ligands, giving rise to a two‐dimensional graphite‐like 6³ layer structure. These two‐dimensional layers are further linked by O—H...O hydrogen‐bonding interactions to form a three‐dimensional supramolecular architecture. The photoluminescence properties of the title compound were also investigated.     

A three‐dimensional ZnII coordination framework: poly[[μ2‐(E)‐1,2‐bis(pyridin‐4‐yl)ethene][μ4‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato][μ2‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato]dizinc(II)]

In the title coordination polymer, [Zn₂(C₁₄H₈N₂O₄)₂(C₁₂H₁₀N₂)]_n, the asymmetric unit contains one Zn^II cation, two halves of 2,2′‐(diazene‐1,2‐diyl)dibenzoate anions (denoted L²⁻) and half of a 1,2‐bis(pyridin‐4‐yl)ethene ligand (denoted bpe). The three ligands lie across crystallographic inversion centres. Each Zn^II centre is four‐coordinated by three O atoms of bridging carboxylate groups from three L²⁻ ligands and by one N atom from a bpe ligand, forming a tetrahedral coordination geometry. Two Zn^II atoms are bridged by two carboxylate groups of L²⁻ ligands, generating a [Zn₂(CO₂)₂] ring. Each loop serves as a fourfold node, which links its four equivalent nodes via the sharing of four L²⁻ ligands to form a two‐dimensional [Zn₂L₄]_n net. These nets are separated by bpe ligands acting as spacers, producing a three‐dimensional framework with a 4⁶6⁴ topology. Powder X‐ray diffraction and solid‐state photoluminescence were also measured.     

A three‐dimensional coordination polymer of 3‐(3,5‐dicarboxybenzyloxy)benzoic acid with zinc

The synthesis is reported of the tricarboxylic acid 3‐(3,5‐dicarboxybenzyloxy)benzoic acid (H₃L) and the product of its reaction under solvothermal conditions with Zn^II cations, namely poly[[μ₆‐3‐(3,5‐dicarboxylatobenzyloxy)benzoato](dimethylformamide)‐μ₃‐hydroxido‐dizinc(II)], [Zn₂(C₁₆H₉O₇)(OH)(C₃H₇NO)]_n, the formation of which is associated with complete deprotonation of H₃L. Its crystal structure consists of a single‐framework coordination polymer of the organic L³⁻ ligand with Zn^II cations in a 1:2 ratio, with additional hydroxide and dimethylformamide (DMF) ligands coordinated to the Zn^II centres. The Zn^II cations are characterized by coordination numbers of 5 and 6, being bridged to each other by hydroxide ligands. In the polymeric framework, the carboxylate‐ and hydroxy‐bridged Zn^II cations are arranged in coordination‐tessellated columns, which propagate along the a axis of the crystal structure, and each L³⁻ ligand links to seven different Zn^II centres via Zn—O bonds of two different columns. The coordination framework, composed of [Zn₂(L)(OH)(DMF)]_n units, forms an open architecture, the channel voids within it being filled by the zinc‐coordinating DMF ligands. This report provides the first structural evidence for the formation of coordination polymers with H₃L via multiple metal–ligand bonds through its carboxylate groups.<!?tpb=21.5pt>     

Syntheses,Structures, and Photophysical Properties of Two Coordination Polymers Based on 2,3‐Dioxo‐1,2,3,4‐tetrahydroquinoxaline‐6‐carboxylic Acid

Two complexes based on the ligand 1,4‐dihydro‐2,3‐quinoxalinedione, namely [Mn(H₂L)₂(H₂O)₂]_n ( 1 ) and {[Zn₂(H₂L)₂(tz)₂] · 5H₂O}_n ( 2 ) (H₃L = 2,3‐dioxo‐1,2,3,4‐tetrahydroquinoxaline‐6‐carboxylic acid, Htz = 1,2,4‐triazole) were hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, as well as single‐crystal and powder X‐ray diffraction. Complex 1 exhibited a 1D comb‐like chain formed by H₂L^– anions linking Mn^II ions, whereas complex 2 was a 2D layer‐like structure with square‐shaped windows and outstretched arms built by combination of H₂L^– and tz^– ligands with Zn^II ions. The adjacent chains or layers connected with each other by intermolecular hydrogen bonding and π–π stacking to further extend to a 3D supermolecular framework. In addition, the thermal stabilities, luminescence properties, and optical energy gap of 1 and 2 were investigated in detail.     

Poly[bis(μ‐benzene‐1,4‐dicarboxylato)bis[μ‐6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline]dilead(II)]: an interpenetrating α‐Po net

The asymmetric unit of the title compound, [Pb₂(C₈H₄O₄)₂(C₁₈H₁₁N₅)₂]_n, contains two Pb^II atoms, two benzene‐1,4‐dicarboxylate (1,4‐bdc) dianions and two 6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline (L) ligands. Each Pb^II atom is eight‐coordinated by three N atoms from two different L ligands and five carboxylate O atoms from three different 1,4‐bdc dianions. The two 1,4‐bdc dianions (1,4‐bdc₁ and 1,4‐bdc₂) show different coordination modes. Each 1,4‐bdc₁ coordinates to two Pb^II atoms in a chelating bis‐bidentate mode. Each carboxylate group of the 1,4‐bdc₂ anion connects two Pb^II atoms in a chelating–bridging tridentate mode to form a dinuclear unit. Neighbouring dinuclear units are connected together by the aromatic backbone of the 1,4‐bdc dianions and the L ligands into a three‐dimensional six‐connected α‐polonium framework. The most striking feature is that two identical three‐dimensional single α‐polonium nets are interlocked with each other, thus leading directly to the formation of a twofold interpenetrated three‐dimensional α‐polonium architecture. The framework is held together in part by strong N—H...O hydrogen bonds between the imidazole NH groups of the L ligands and the carboxylate O atoms of 1,4‐bdc dianions within different α‐polonium nets.     

Syntheses,Structures and Characterization of Four Metal‐Organic Frameworks constructed by 2,2′,6,6′‐Tetramethoxy‐4,4′‐biphenyldicarboxylic Acid

Four metal‐organic frameworks (MOFs), {[Mn_3.5L(OH)(HCOO)₄(DMF)] · H₂O} ( 1 ), {[In_2.5L₂O(OH)_1.5(H₂O)₂] · DMF · CH₃CN · 2H₂O} ( 2 ), {[Pb₄L₃O(DMA)] · CH₃CN} ( 3 ), and {[LaL(NO₃)(DMF)₂] · 2H₂O} ( 4 ) were synthesized by utilizing the ligand 2,2′,6,6′‐tetramethoxy‐4,4′‐biphenyldicarboxylic acid (H₂L) via solvothermal methods. All MOFs were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction, thermogravimetric analysis, and infrared spectroscopy. In 1 , the Mn²⁺ ions are interconnected by formic groups in situ produced via DMF decomposition to form a rare 2D macrocyclic plane, which is further linked by L^2– to construct the final 3D network. In 2 , 1D zip‐like infinite chain is formed and then interconnected to build the 3D framework. In 3 , a [Pb₆(μ₄‐O)₂(O₂C)₁₀(DMA)₂] cluster with a centrosymmetric [Pb₆(μ₄‐O)₂]⁸⁺ octahedral core is formed in the 3D structure. In 4 , the La³⁺ ions are connected with each other through carboxylate groups of L^2– to generate 1D zigzag chain, which is further linked by L^2– to construct a 3D network with sra topology. Solid photoluminescence properties of 3 and 4 were also investigated.     

Poly[(N,N‐dimethylformamide‐κO)(μ3‐4,4′‐ethylenedibenzoato‐κ5O,O′:O′:O′′,O′′′)(pyrazino[2,3‐f][1,10]phenanthroline‐κ2N8,N9)lead(II)]

In the title Pb^II coordination polymer, [Pb(C₁₆H₁₀O₄)(C₁₄H₈N₄)(C₃H₇NO)]_n, each Pb^II atom is eight‐coordinated by two chelating N atoms from one pyrazino[2,3‐f][1,10]phenanthroline (L) ligand, one dimethylformamide (DMF) O atom and five carboxylate O atoms from three different 4,4′‐ethylenedibenzoate (eedb) ligands. The eedb dianions bridge neighbouring Pb^II centres through four typical Pb—O bonds and one longer Pb—O interaction to form a two‐dimensional structure. The C atoms from the L and eedb ligands form C—H...O hydrogen bonds with the O atoms of eedb and DMF ligands, which further stabilize the structure. The title compound is the first Pb^II coordination polymer incorporating the L ligand.     

catena‐Poly[[bis[5‐(4‐pyridyl‐κN)‐2‐(2‐pyridylmethylsulfanyl)‐1,3,4‐oxadiazole]cadmium(II)]‐di‐μ‐thiocyanato‐κ2N:S;κ2S:N]

The title compound, [Cd(NCS)₂(C₁₃H₁₀N₄OS)₂]_n, contains SCN⁻ anions acting as end‐to‐end bridging ligands which utilize both S and N atoms to link cadmium(II) centers into one‐dimensional double chains. The multidentate 5‐(4‐pyridyl)‐2‐(2‐pyridylmethylsulfanyl)‐1,3,4‐oxadiazole ligands behave as monodentate terminal ligands, binding metal centers only through the N atoms of the 4‐pyridyl groups. Two types of eight‐membered rings are formed by two SCN⁻ anions bridging Cd^II centers, viz. planar and chair conformation, which are alternately disposed along the same chain. Finally, chains define a two‐dimensional array through two different interchain π–π stacking interactions.     

(3,4)‐Connected Twofold Interpenetrated Network with Right‐ and Left‐Handed Helical Chains: Synthesis,Crystal Structure,and Luminescence Sensing

The zinc(II) coordination polymer Zn₂(L)₂(bix)₂ · 2H₂O ( 1 ) [H₂L = 4,4′‐methylenebis(oxy)dibenzoic acid, bix = 1,4‐bis(imidazole‐1‐yl‐methylene)‐benzene] was synthesized by hydrothermal reaction. The title compound was characterized by single‐crystal X‐ray diffraction analysis, IR spectroscopy, and elemental analysis. The crystal structure determination reveals that compound 1 displays a twofold interpenetrated 3D framework, in which the Zn atoms are connected by the H₂L ligands into interesting right and left‐handed helical chains. Topological analysis reveals that the title compound displays a (3,4)‐connected (6³) (6⁵ · 8) topology. The solid‐state luminescent spectra was studied. Furthermore, the dispersed solution of compound 1 in DMF exhibits strong fluorescent emission, which could be quenched by trace amount of nitrobenzene.     

Poly[bis(μ4‐benzene‐1,2‐dicarboxylato)di‐μ3‐isonicotinato‐dilanthanum(III)]

In the title compound, [La₂(C₈H₄O₄)₂(C₆H₄NO₂)₂]_n, there are two crystallographically independent La centres, both nine‐coordinated in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom. The La centres are linked by the carboxylate groups of isonicotinate (IN⁻) and benzene‐1,2‐dicarboxylate (BDC²⁻) ligands to form La–carboxylate chains, which are further expanded into a three‐dimensional framework with nanometre‐sized channels by La—N bonds. In the construction of the resultant architecture, in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom, while the BDC ligands link to four different cations each, displaying penta‐ and heptadentate chelating–bridging modes, respectively.     

Observation of a Less Stable Conformer of N,N′‐Piperazine‐bis(methylenephosphonate) Ligand in a Six‐coordinated ­Samarium Phosphonate Framework

The three‐dimensional (3D) samarium phosphonate framework [Sm₂(H₂L)₃]_n · 5n(H₂O) ( 1 ) [H₄L = N,N′‐piperazine‐bis(methylenephosphonic acid)] was synthesized by hydrothermal reaction of Sm₂O₃ with N,N′‐piperazine‐bis(methylenephosphonic acid) hydrochloride in the presence of glutaric acid. Single‐crystal X‐ray diffraction analysis reveals that it has a 3D open framework structure with helical channels along the crystallographic c axis. The channels are filled up by discrete pentameric water clusters, which are hydrogen‐bonded to the host. Compound 1 displays two interesting structural features: (a) two of three H₂L^2– ligands adopt the less stable a,e‐cis conformation; (b) both of the Sm^III ions exhibit rather unusual octahedral coordination arrangements. In addition, the photoluminescent property was investigated.     

The crystal structure and photocatalytic properties of a three‐dimensional cadmium(II) metal–organic framework: poly[bis(μ3‐benzene‐1,2‐dicarboxylato)[μ2‐1,4‐bis(pyridin‐3‐ylmethoxy)benzene]dicadmium(II)]

Photocatalysis is a green technology for the treatment of all kinds of contaminants and has advantages over other treatment methods. Recently, much effort has been devoted to developing new photocatalytic materials based on metal–organic frameworks for use in the degradation of many kinds of organic contaminants. With the aim of searching for more effective photocatalysts, the title three‐dimensional coordination polymer, [Cd₂(C₈H₄O₄)₂(C₁₈H₁₆N₂O₂)]_n, was prepared. The asymmetric unit contains one Cd^II cation, one benzene‐1,2‐dicarboxylate anion (denoted L²⁻) and half of a centrosymmetric 1,4‐bis(pyridin‐3‐ylmethoxy)benzene ligand (denoted bpmb). Each Cd^II centre is five‐coordinated by four carboxylate O atoms from two L²⁻ ligands and by one N atom from a bpmb ligand, forming a disordered pentagonal pyramidal coordination geometry. The Cd^II centres are interlinked by L²⁻ ligands to form a one‐dimensional [Cd₂L₂]_n chain. Adjacent chains are further connected by bpmb linkers, giving rise to a two‐dimensional network, and these networks are pillared by bpmb to afford a three‐dimensional framework with a 3³.4².6³.7¹.8¹ topology. Each grid in the framework has large channels which are filled mainly by the two other equivalent frameworks to form a threefold interpenetrating net. The compound exhibits relatively good photocatalytic activity towards the degradation of methylene blue in aqueous solution under UV irradiation.     

A one‐dimensional silver(I) coordination polymer based on an asymmetric flexible N‐donor carboxylate ligand: catena‐poly[(μ3‐4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoato‐κ3O:O′:N4)silver(I)]

The title compound, [Ag(C₁₅H₁₁N₄O₂S)]_n, was synthesized by the reaction of 4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoic acid (Hptmba) with silver nitrate and triethylamine at room temperature. The asymmetric unit contains one crystallographically independent Ag^I cation and one ptmba⁻ ligand. Each Ag^I cation is tricoordinated by two carboxylate O atoms and one tetrazole N atom from three different ptmba⁻ ligands, displaying a distorted T‐shaped geometry. Three Ag^I cations are linked by tris‐monodentate bridging ptmba⁻ ligands to form a one‐dimensional double chain along the c axis, which is further consolidated by an intrachain π–π contact with an offset face‐to‐face distance of 4.176 (3) Å between the centroids of two adjacent aromatic rings in neighbouring benzoate groups. The one‐dimensional chains are linked into a three‐dimensional supramolecular framework by additional π–π interchain interactions, viz. of 3.753 (3) Å between two phenyl substituents of the tetrazole rings and of 4.326 (2) Å between a benzoate ring and a tetrazole ring. Thermogravimetric analysis and the fluorescence spectrum of the title compound reveal its good thermal stability and a strong green luminescence at room temperature.     

FeIII in a low‐spin state in caesium bis[3‐ethoxysalicylaldehyde 4‐methylthiosemicarbazonato(2–)‐κ3O2,N1,S]ferrate(III) methanol monosolvate

The synthesis and crystal structure (at 100 K) of the title compound, Cs[Fe(C₁₁H₁₃N₃O₂S₂)₂]·CH₃OH, is reported. The asymmetric unit consists of an octahedral [Fe^III(L)₂]⁻ fragment, where L²⁻ is 3‐ethoxysalicylaldehyde 4‐methylthiosemicarbazonate(2−) {systematic name: [2‐(3‐ethoxy‐2‐oxidobenzylidene)hydrazin‐1‐ylidene](methylamino)methanethiolate}, a caesium cation and a methanol solvent molecule. Each L²⁻ ligand binds through the thiolate S, the imine N and the phenolate O atoms as donors, resulting in an Fe^IIIS₂N₂O₂ chromophore. The O,N,S‐coordinating ligands are orientated in two perpendicular planes, with the O and S atoms in cis positions and the N atoms in trans positions. The Fe^III cation is in the low‐spin state at 100 K.     

Topological identification of the first uninodal 8‐connected lsz MOF built from 2,2′‐difluorobiphenyl‐4,4′‐dicarboxylate pillars and cadmium(II)–triazolate layers

Using polynuclear metal clusters as nodes, many high‐symmetry high‐connectivity nets, like 8‐connnected bcu and 12‐connected fcu , have been attained in metal–organic frameworks (MOFs). However, construction of low‐symmetry high‐connected MOFs with a novel topology still remains a big challenge. For example, a uninodal 8‐connected lsz network, observed in inorganic ZrSiO₄, has not been topologically identified in MOFs. Using 2,2′‐difluorobiphenyl‐4,4′‐dicarboxylic acid (H₂L) as a new linker and 1,2,4‐triazole (Htrz) as a coligand, a novel three‐dimensional Cd^II–MOF, namely poly[tetrakis(μ₄‐2,2′‐difluorobiphenyl‐4,4′‐dicarboxylato‐κ⁵O¹,O^1′:O^1′:O⁴:O^4′)tetrakis(N,N‐dimethylformamide‐κO)tetrakis(μ₃‐1,2,4‐triazolato‐κ³N¹:N²:N⁴)hexacadmium(II)], [Cd₆(C₁₄H₆F₂O₄)₄(C₂H₂N₃)₄(C₃H₇NO)₄]_n, (I), has been prepared. Single‐crystal structure analysis indicates that six different Cd^II ions co‐exist in (I) and each Cd^II ion displays a distorted [CdO₄N₂] octahedral geometry with four equatorial O atoms and two axial N atoms. Three Cd^II ions are connected by four carboxylate groups and four trz⁻ ligands to form a linear trinuclear [Cd₃(COO)₄(trz)₄] cluster, as do the other three Cd^II ions. Two Cd₃ clusters are linked by trz⁻ ligands in a μ_1,2,4‐bridging mode to produce a two‐dimensional Cd^II–triazolate layer with (6,3) topology in the ab plane. These two‐dimensional layers are further pillared by the L²⁻ ligands along the c axis to generate a complicated three‐dimensional framework. Topologically, regarding the Cd₃ cluster as an 8‐connected node, the whole architecture of (I) is a uninodal 8‐connected lsz framework with the Schläfli symbol (4²²·6⁶). Complex (I) was further characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction, thermogravimetric analysis and a photoluminescence study. MOF (I) has a high thermal and water stability.