A new two‐dimensional extended adenine and thiophenecarboxylate mixed‐ligand zinc(II) complex: synthesis,structure, thermostability and luminescent properties

The design and preparation of crystalline polymeric materials has attracted increasing attention due to their diverse applications as functional materials in gas storage, separation, catalysis, sensing and photoluminescence. The judicious selection of organic linkers is critical for varying the coordination behaviour of the metal ions and determining the overall characteristics of the networks. A new adenine‐based Zn^II coordination polymer, [Zn(C₆H₂O₄S)(C₅H₅N₅)]_n or [Zn(tdc)(9H‐ade)] (H₂tdc is thiophene‐2,5‐dicarboxylic acid and ade is adenine), has been prepared hydrothermally and the crystal structure exhibits in its packing two‐dimensional (4,4) grid sheets parallel to the ab plane, featuring two distinct square cavities delimited by the two types of ligands and the Zn^II ions with the dimensions 6.6 × 6.6 and 10.2 × 10.2 Å (based on the Zn...Zn distance). The title complex shows enhanced photoluminescence at 378 nm compared to the free ligands, suggesting that the coordination of H₂tdc or adenine to the metal centre effectively increases the rigidity of the ligands and reduces the energy loss by radiative decay of intraligand excited states.     

BN-Doped Metal–Organic Frameworks: Tailoring 2D and 3D Porous Architectures through Molecular Editing of Borazines

Building on the MOF approach to prepare porous materials, herein we report the engineering of porous BN-doped materials using tricarboxylic hexaarylborazine ligands, which are laterally decorated with functional groups at the full-carbon ‘inner shell’. Whilst an open porous 3D entangled structure could be obtained from the double interpenetration of two identical metal frameworks derived from the methyl substituted borazine, the chlorine-functionalised linker undergoes formation of a porous layered 2D honeycomb structure, as shown by single-crystal X-ray diffraction analysis. In this architecture, the borazine cores are rotated by 60° in alternating layers, thus generating large rhombohedral channels running perpendicular to the planes of the networks. An analogous unsubstituted full-carbon metal framework was synthesised for comparison. The resulting MOF revealed a crystalline 3D entangled porous structure, composed by three mutually interpenetrating networks, hence denser than those obtained from the borazine linkers. Their microporosity and CO₂ uptake were investigated, with the porous 3D BN-MOF entangled structure exhibiting a large apparent BET specific surface area (1091 m² g⁻¹) and significant CO₂ reversible adsorption (3.31 mmol g⁻¹) at 1 bar and 273 K.     

Preparation,characterization, and properties of two rare earth organic frameworks with 1H-benzimidazole-2-carboxylic acid

Reaction of rare earth metal ions with 1H-benzimidazole-2-carboxylic acid (H₂BIC) acid yielded two rare earth organic frameworks [Ln(HBIC)₃] _n (Ln?=?Gd 1, Y 2; H₂BIC) under hydrothermal conditions. Both compounds were structurally characterized by single-crystal X-ray diffraction. Their thermal stabilities, luminescent, and magnetic properties were also investigated. Compounds 1 and 2 are isomorphic and present 2-D networks constructed by bridging-chelating HBIC^? linkers and rare earth cation nodes, in which each asymmetric unit consists of one crystallographically unique Ln(III) ion and three HBIC^? with two kinds of coordination modes. The two compounds exhibit high-thermal stability, stable to 320?°C. Antiferromagnetic interactions between Gd(III) centers for 1 were observed from magnetic susceptibility data. 2 exhibits a strong blue emission band in the solid state.     

Charged Porous Polymers using a Solid CO Cross‐Coupling Reaction

Herein, we report a green, fast, efficient mechanochemical strategy for charged porous polymers (CPPs). A cationic CPP with basic anions and an anionic CPP with Li⁺ cations were fabricated by solid grinding under solvent‐free conditions. Compared with solution‐based synthesis, mechanochemical grinding can shorten the reaction time from dozens of hours to several minutes (60–90 min) to form polymers possessing a high molecular mass and low polydispersity. During the construction of CPPs, a Pd‐catalyzed solid polycondensation based on unactivated organic linkers was introduced. In particular, CPPs with basic phenolic or proline anions showed good activity and stability in SO₂ capture, and Li⁺‐functionalized CPPs can be post‐modified to CPPs with other metal ions by ion exchange, highlighting the tailorable feature of ionic‐modified CPPs.     

A series of isostructural mesoporous metal-organic frameworks obtained by ion-exchange induced single-crystal to single-crystal transformation

A series of metal-organic frameworks representing a non-interpenetrated framework analogue of MOF-14 have been synthesized by using two different linkers, 4,4',4'-benzene-1,3,5-triyl-benzoic acid (H(3)BTB) and 4,4'-bipyridine (Bpy). Interestingly, the transition metal ions in the paddle-wheel metal clusters could be exchanged by other transition metal ions via a direct single-crystal to single-crystal transformation. This post-synthesis route can be used for synthesis of isomorphous metal-organic frameworks that cannot be obtained by direct synthesis.     

Iodine-Chemisorption,Interpenetration and Polycatenation: Cationic MOFs and CPs from Group 13 Metal Halides and Di-Pyridyl-Linkers

Eight cationic, two-dimensional metal-organic frameworks (MOFs) were synthesized in reactions of the group 13 metal halides AlBr₃, AlI₃, GaBr₃, InBr₃ and InI₃ with the dipyridyl ligands 1,2-di(4-pyridyl)ethylene (bpe), 1,2-di(4-pyridyl)ethane (bpa) and 4,4’-bipyridine (bipy). Seven of them follow the general formula ²_∞[MX₂(L)₂]A, M=Al, In, X=Br, I, A⁻=[MX₄]⁻, I⁻, I₃⁻, L=bipy, bpa, bpe. Thereby, the porosity of the cationic frameworks can be utilized to take up the heavy molecule iodine in gas-phase chemisorption vital for the capture of iodine radioisotopes. This is achieved by switching between I⁻ and the polyiodide I₃⁻ in the cavities at room temperature, including single-crystal-to-single-crystal transformation. The MOFs are 2D networks that exhibit (4,4)-topology in general or (6,3)-topology for ²_∞[(GaBr₂)₂(bpa)₅][GaBr₄]₂⋅bpa. The two-dimensional networks can either be arranged to an inclined interpenetration of the cationic two-dimensional networks, or to stacked networks without interpenetration. Interpenetration is accompanied by polycatenation. Due to the cationic character, the MOFs require the counter ions [MX₄]⁻, I⁻ or I₃⁻ counter ions in their pores. Whereas the [MX₄]⁻, ions are immobile, iodide allows for chemisorption. Furthermore, eight additional coordination polymers and complexes were identified and isolated that elaborate the reaction space of the herein reported syntheses.     

Two New Zinc(II) Coordination Polymers Based on 1, 6‐Bis(2‐methyl‐imidazole‐1‐yl)‐hexane Ligand: Synthesis,Structures, and Properties

Two coordination polymers based on 1, 6‐bis(2‐methyl‐imidazole‐1‐yl)‐hexane (bimh), namely {[Zn₃(BTC)₂(bimh)] · (bimh)}_n ( 1 ) and {[Zn(IPA)(bimh)] · (CH₃CH₂OH)_0.5}_n ( 2 ) (H₃BTC = trimesic acid, H₂IPA = isophthalic acid), were synthesized through hydrothermal reactions. In compound 1 , the zinc(II) ions are bridged by BTC^3– ligands to form an undulating infinite two‐dimensional (2D) polymeric network. The 3D networks of 1 show a twofold interpenetrating net. In compound 2 , zinc(II) ions are bridged by IPA^2– ligands to form one‐dimensional (1D) helical structures. The 2D structures of 2 are further assembled into 3D networks through aromatic π–π stacking interactions. Both compounds exhibit strong photoluminescence at room temperature and may be good candidates for potential luminescence materials.     

Metal–Organic Perovskites: Synthesis,Structures, and Magnetic Properties of [C(NH2)3][MII(HCOO)3] (M=Mn,Fe, Co,Ni, Cu,and Zn; C(NH2)3= Guanidinium)

We report the synthesis, crystal structures, and spectral, thermal, and magnetic properties of a family of metal–organic perovskite ABX₃, [C(NH₂)₃][M^II(HCOO)₃], in which A=C(NH₂)₃ is guanidinium, B=M is a divalent metal ion (Mn, Fe, Co, Ni, Cu, or Zn), and X is the formate HCOO^?. The compounds could be synthesized by either diffusion or hydrothermal methods from water or water‐rich solutions depending on the metal. The five members (Mn, Fe, Co, Ni, and Zn) are isostructural and crystallize in the orthorhombic space group Pnna, while the Cu member in Pna2₁. In the perovskite structures, the octahedrally coordinated metal ions are connected by the anti–anti formate bridges, thus forming the anionic NaCl‐type [M(HCOO)₃]^? frameworks, with the guanidinium in the nearly cubic cavities of the frameworks. The Jahn–Teller effect of Cu²⁺ results in a distorted anionic Cu–formate framework that can be regarded as Cu–formate chains through short basal Cu? O bonds linked by the long axial Cu? O bonds. These materials show higher thermal stability than other metal–organic perovskite series of [AmineH][M(HCOO)₃] templated by the organic monoammonium cations (AmineH⁺) as a result of the stronger hydrogen bonding between guanidinium and the formate of the framework. A magnetic study revealed that the five magnetic members (except Zn) display spin‐canted antiferromagnetism, with a Néel temperature of 8.8 (Mn), 10.0 (Fe), 14.2 (Co), 34.2 (Ni), and 4.6 K (Cu). In addition to the general spin‐canted antiferromagnetism, the Fe compound shows two isothermal transformations (a spin‐flop and a spin‐flip to the paramagnetic phase) within 50 kOe. The Co member possesses quite a large canting angle. The Cu member is a magnetic system with low dimensional character and shows slow magnetic relaxation that probably results from the domain dynamics.     

Relation between the crystal structures of some salts of the type Me(OCOCH3)2 · nH2O and their ability to form mixed crystals or double salts (Me2+ = Mg,Ca, Mn,Co, Ni,Cu, Zn,Cd)

An attempt is made to find the relation between the crystal structures of some salts of the type Me(OCOCH₃)₂ · nH₂O (Me²⁺ = Mg, Ca, Mn, Co, Ni, Cu, Zn, Cd) and their ability to form mixed crystals or double salts by taking into account the difference in the ground-state configurations of the metal (II) ions. Such a treatment is based on the theoretical argument that the formation of isomorphous and isodimorphous mixed crystals occurs when the admixed ion may assume the coordination environment of the substituted ion in the crystal structure of the host salt. Double salts are formed mainly between the acetates of the d⁵, d¹⁰ and p⁶ metal ions, i.e., for ions that allow strong angular deformations of the coordination polyhedra or when at least one of the metal ions meets this condition so that acetate bridge bonding may occur.     

A Linker‐Mediated Self‐Assembly Method to Couple Isocharged Nanostructures: Layered Double Hydroxide–CdS Nanohybrids with High Activity for Visible‐Light‐Induced H2 Generation

The electrostatically derived self‐assembly of cationic Zn‐Cr‐layered double hydroxide (LDH) nanosheets and cationic CdS quantum dots (QDs) with anionic linkers leads to the formation of strongly coupled Zn‐Cr‐LDH–CdS nanohybrids. The hybridization with Zn‐Cr‐LDH leads to significant enhancement of the photocatalytic activity of CdS for visible‐light‐induced H₂ generation, a property that is attributed to the depression of electron–hole recombination. In comparison with a direct hybridization method between oppositely charged species, this linker‐mediated method provides greater flexibility in controlling the chemical composition and electronic coupling of the nanohybrids. The present hybridization strategy provides a useful method not only to couple two kinds of isocharged nanostructured materials, but also to explore efficient hybrid‐type photocatalysts.     

A stable pillared metal–organic framework constructed by H4TCPP ligand as luminescent sensor for selective detection of TNP and Fe3+ ions

A novel luminescent metal–organic framework ( Zn‐TCPP/BPY ) with pillared structure based on 2,3,5,6‐tetrakis(4‐carboxyphenyl)pyrazine (H₄TCPP) and 4,4′‐bipyridine (BPY) has been designed and synthesized through a solvothermal reaction. The [Zn₂(COO)₄] paddlewheel units are linked by TCPP^4? ligands to form two‐dimensional layers and further connected by BPY ligands as pillars to construct the twofold interpenetrating three‐dimensional framework. Interestingly, Zn‐TCPP/BPY possesses outstanding stability in organic solvents and water as well as maintains its structural rigidity in aqueous solutions of different pH values (3–12). After activation, Zn‐TCPP/BPY possesses permanent porosity with Brunauer–Emmett–Teller surface area of 630 m² g^–1. Remarkably, Zn‐TCPP/BPY displays excellent fluorescent property in virtue of the aggregation‐induced emission effect of the H₄TCPP ligand, which can be highly active and quenched by small amounts of 2,4,6‐trinitrophenol (TNP) and Fe³⁺ ions. Furthermore, the detection effect of Zn‐TCPP/BPY remains basically the same even after five cycles. The excellent stability, high sensitivity, and recyclability of Zn‐TCPP/BPY make it an outstanding chemical sensor for detecting TNP and Fe³⁺ ions.     

A fivefold interpenetrating diamond‐like three‐dimensional metal–organic framework: poly[(μ2‐benzene‐1,4‐diacetato)[μ2‐1,6‐bis(1,2,4‐triazol‐1‐yl)hexane]zinc(II)]

In the mixed‐ligand metal–organic title polymeric compound, [Zn(C₁₀H₈O₄)(C₁₀H₁₆N₆)]_n or [Zn(PBEA)(BTH)]_n [H₂PBEA is benzene‐1,4‐diacetic acid and BTH is 1,6‐bis(1,2,4‐triazol‐1‐yl)hexane], the asymmetric unit contains a Zn^II atom, one half of a BTH ligand and one half of a doubly deprotonated H₂PBEA ligand. Each Zn^II centre lies on a crystallographic twofold rotation axis and is four‐coordinated by two O atoms from two distinct PBEA²⁻ ligands and two N atoms from two different BTH ligands in a {ZnO₂N₂} coordination environment. The three‐dimensional topology of the title compound corresponds to that of a fivefold interpenetrating diamond‐like metal–organic framework.     

A series of 1-D zinc(II) coordination polymers with 3-D supramolecular networks: synthesis,structural investigation,and NBO analysis

Abstract

N,N′-Bis(pyridin-4-ylmethylene)naphthalene-1,5-diamine (L) acts as a bipyridine analogue linker ligand towards {Zn₇(μ₄-O)₂(OAc)₁₀}, {Zn₂(NCS)₂(OAc)₂}, and {Zn(N₃)₂} nodes and allows construction of three new 1-D coordination polymers, the linear chain [Zn₇(μ₄-O)₂(OAc)₁₀(L)]_n (1), [Zn(NCS)(OAc)(L)]_n (2) in ladder-type geometry and the zigzag chain [Zn(N₃)₂(L)]_n (3). Structural characterization reveals that in 1 acetate anionic ligands connect seven Zn(II) ions through the bridging coordination modes μ₃-η¹,η² and μ₂-η¹,η¹. The resulting heptanuclear node is located on an inversion center and therefore consists of four crystallographically distinct cations; their coordination spheres correspond to distorted octahedra or tetrahedra. The Zn(II) ions in polymer 2 exhibit distorted trigonal bipyramidal {ZnN₃O₂} coordination; μ₂-η¹,η¹ coordinated acetate and terminal thiocyanate ligands lead to inversion-symmetric [Zn₂(NCS)₂(OAc)₂] secondary building units (SBU), which are further linked by the N,N′-bipyridine analogue L. Terminal coordination of two anionic azide ligands and the bridging bipyridine L result in coordination polymer 3, in which the cations adopt distorted tetrahedral {ZnN₄} coordination. In all crystalline solids 1–3, adjacent 1-D chains interact through π–π stacking and non-classical (C???H···O, C???H···π) hydrogen bonds, leading to 3-D supramolecular architectures. Differences in their 3-D arrangement are due to variations in the anionic co-ligands, subtle conformational differences in the semi-rigid linker and the variable coordination sphere about the zinc cations. Thermogravimetric investigations indicate differences in both thermal stability and decomposition mode. Natural bond orbital (NBO) analysis provides a convenient basis for investigating the intramolecular bonding interactions and delocalization effects in these molecular systems. Finally, solids 1–3 exhibit intense luminescence at room temperature.     

A Microporous Anionic Metal–Organic Framework for Sensing Luminescence of Lanthanide(III) Ions and Selective Absorption of Dyes by Ionic Exchange

Herein, a novel anionic framework with primitive centered cubic (pcu) topology, [(CH₃)₂NH₂]₄[(Zn₄dttz₆)Zn₃]?15 DMF?4.5 H₂O, ( IFMC‐2 ; H₃dttz=4,5‐di(1H‐tetrazol‐5‐yl)‐2H‐1,2,3‐triazole) was solvothermally isolated. A new example of a tetranuclear zinc cluster {Zn₄dttz₆} served as a secondary building unit in IFMC‐2 . Furthermore, the metal cluster was connected by Zn^II ions to give rise to a 3D open microporous structure. The lanthanide(III)‐loaded metal–organic framework (MOF) materials Ln³⁺@IFMC‐2 , were successfully prepared by using ion‐exchange experiments owing to the anionic framework of IFMC‐2 . Moreover, the emission spectra of the as‐prepared Ln³⁺@IFMC‐2 were investigated, and the results suggested that IFMC‐2 could be utilized as a potential luminescent probe toward different Ln³⁺ ions. Additionally, the absorption ability of IFMC‐2 toward ionic dyes was also performed. Cationic dyes can be absorbed, but not neutral and anionic dyes, thus indicating that IFMC‐2 exhibits selective absorption toward cationic dyes. Furthermore, the cationic dyes can be gradually released in the presence of NaCl.     

Synthesis,electrochemical, in situ spectroelectrochemical and in situ electrocolorimetric characterization of new phthalocyanines peripherally fused to four flexible crown ether moieties

Novel Ni(II), Zn(II), Co(II) and Cu(II) phthalocyanines with four peripheral 4-[methyleneoxy(18-crown-6)] groups have been synthesized via the cyclic tetramerization of 4-[{(18-crown-6)-yl}methyleneoxy]phthalonitrile and the corresponding metal salts (NiCl₂, Zn(CH₃COO)₂, CoCl₂ and CuCl₂). The thermal stabilities of the metal-free and metallophthalocyanine compounds were determined by thermogravimetric analysis. The structures of the target compounds were confirmed using elemental analysis, IR, ¹H-NMR, ¹³C-NMR, UV–Vis and MS spectral data. Voltammetric and in situ spectroelectrochemical measurements show that while the cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, the metal-free, nickel, zinc and copper phthalocyanines show only ring-based reduction and oxidation processes. An in situ electrocolorimetric method has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes.     

[Fe19] “Super‐Lindqvist” Aggregate and Large 3D Interpenetrating Coordination Polymer from Solvothermal Reactions of [Fe2(OtBu)6] with Ethanol

The syntheses, crystal structures, and physical properties of [HFe₁₉O₁₄(OEt)₃₀] and {Fe₁₁(OEt)₂₄}_∞ are reported. [HFe₁₉O₁₄(OEt)₃₀] has an octahedral shape. Its core with a central Fe metal ion surrounded by six μ₆‐oxo ligands is arranged in the rock salt structure. {Fe₁₁(OEt)₂₄}_∞ is a mixed‐valence coordination polymer in which Fe^III metal ions form three 3D interpenetrating (10,3)‐b nets. The arrangement of the Fe^III ions can also be compared to that of Si ions in α‐ThSi₂. Thus, the described structures are at the interface between molecular and solid‐state chemistry.     

Synthesis,characterization, and catalytic activity of heterometallic ion-pair Ni/Mn and Ni/Zn complexes

Two new heterometallic compounds, [Ni(bpy)₃][Mn(NCO)₄]·H₂O (1) and [Ni(phen)₃]₂[Zn(NCO)₄]₂·4DMSO·H₂O (2) [bpy?=?2,2′-bipyridine and phen?=?1,10-phenanthroline], have been synthesized and characterized. The structures of 1 and 2 were solved by single-crystal X-ray diffraction analysis. The cationic moieties of [Ni(bpy)₃]²⁺ in 1 and [Ni(phen)₃]²⁺ in 2 show octahedral environments around Ni(II), whereas the anionic groups of [Mn(NCO)₄]^2? in 1 and [Zn(NCO)₄]^2? in 2 exhibit tetrahedral geometry around the Mn(II) and Zn(II), respectively. Both compounds are catalysts in the H/D exchange of salicylaldehyde in DMSO-d₆ which takes place under mild conditions and short reaction time.     

Discrete Rectangles,Prisms, and Heterometallic Cages from a Conjugated Cp*Rh‐Based Building Block

By carefully selecting an existing synthetic strategy and suitable coordination subunits, constructing desired coordination geometries is no longer that difficult to accomplish. Herein, a new strategy to construct a series of unprecedented structures by using conjugated Cp*Rh‐based complex BN‐OTf (Cp*=η⁵‐C₅Me₅) as the building block is proposed. DFT calculations revealed extensive delocalized π bonds in the subunit. With BN‐OTf , rectangular macrocycles TN‐bpy and TN‐bpe were controllably synthesized. Single‐crystal XRD studies confirmed one‐dimensional stacking channels for the tetranuclear structure. Notably, the starting ligand imidazole‐4,5‐dicarboxylate was found to act not only as a tetradentate but also as a hexadentate ligand that can coordinate to further metal ions. Subsequently, [4 Rh+1 M] heterometallic complexes HMZ (M=Cu and Zn) were accessed by chelating borderline hard/soft Lewis acids. With TN‐Linker or HMZ , two routes resulted in the [8 Rh+2 M] heterometallic cages HMC (M=Cu and Zn) with excellent crystallinity and stability. Surprisingly, when BN‐OTf bonded to rhodium itself, triangular prisms TP‐Linker were obtained with high solubility after being linked by bipyridine linkers. Both the X‐ray structure and ¹H NMR spectrum confirmed the novel isomerization of the triangular structures. All of the compounds were obtained in high yields and were fully characterized by ¹H NMR spectroscopy, elemental analysis, IR spectroscopy, and in most cases single‐crystal X‐ray structure determination.     

Single-Crystal Transformation Engineering the Spin Change of Metal–Organic Frameworks via Cluster Deconstruction

Spin crossover (SCO) materials with new architectures will expand and enrich the research in the SCO field. Here, we report two metal–organic frameworks (MOFs) containing tetradentate organic ligands and hexatopic linkers [Ag₈X₈(CN)₆]⁶⁻ (X=Br and I), which represents the first SCO MOF with clusters as building blocks. The silver halide cluster can be further removed after reacting with lithium tetracyanoquinodimethan (LiTCNQ). Such post-synthetic modification (PSM) is realized via single-crystal to single-crystal (SCSC) transformation from urk to nbo topology. Accordingly, the spin state and fluorescence properties are greatly modified by cluster deconstruction. Therefore, these achievements will provide new ideas for the design of new SCO systems and the development of PSM methods.     

Synthesis,Structures, and Photoluminescence Properties of Five Novel Zinc(II) and Cadmium(II) Coordination Polymers based on Different Zwitterionic Pyridine Ligands

A series of five new Zn^II and Cd^II mixed‐ligand coordination polymers, namely, {[Zn(L₁)(4,4′‐bpy)] · (ClO₄) · 2H₂O} ( 1 ), {[Zn(L₂)(4,4′‐bpy)_0.5] · (ClO₄)} ( 2 ), {[Zn(L₃)(4,4′‐bpy)] · (NO₃) · 2H₂O} ( 3 ), {[Cd(L₄)(4,4′‐bpy)_0.5(NO₃)] · 5H₂O} ( 4 ), and {[Zn(L₄)(4,4′‐bpy)] · Cl · H₂O} ( 5 ) [4,4′‐bpy = 4,4′‐bipyridine, L₁ = 4‐carboxy‐1‐(4‐carboxybenzyl)pyridin‐1‐ium chloride, L₂ = 3‐carboxy‐1‐(4‐carboxybenzyl)pyridin‐1‐ium chloride, L₃ = 4‐carboxy‐1‐(3‐carboxybenzyl)pyridin‐1‐ium chloride, and L₄ = 3‐carboxy‐1‐(3‐carboxybenzyl)pyridin‐1‐ium chloride], were obtained by the reactions of the 4,4′‐bipyridine with four dicarboxylate zwitterionic pyridine ligands. Single‐crystal X‐ray structural analyses reveal that the five complexes demonstrate different molecular frameworks coming from various coordination modes and flexibilities of different dicarboxylate zwitterionic pyridine ligands and central metal atoms. Mononuclear twofold dinuclear 2D twofold interpenetrating net for 2 , four‐coordinate mononuclear twofold interpenetrating 2D layer for 3 , mononuclear 2D layer arranged in parallel and with large grids for 4 , and twofold trans interpenetrating 2D network for compound 5 . The structural diversities in 1 – 5 indicate that the nature of the ligands and the presence of different metal atoms have a great influence on central metal coordination modes and the structural topologies of the metal‐organic molecular architectures. In addition, π ··· π stacking interactions also play important roles in the final crystal packing and supramolecular frameworks. The powder X‐ray diffraction, elemental analysis, and photoluminescence properties of 1 – 5 were studied, which show that architectures play an important role in emission bands and intensities.