3D–2D–0D Stepwise Deconstruction of a Water Framework Templated by a Nanoporous Organic–Inorganic Hybrid Host

The supramolecular salt [H₂pip]₃[Ge(hedp)₂]?14 H₂O ( 1 ) [H₂pip²⁺=piperazine cation C₄H₁₂N₂²⁺; hedp^5?=deprotonated form of etidronic acid, C₂H₃P₂O₇^5?) is reported. This consists of an organic–inorganic hybrid hydrogen‐bonded nanoporous framework, the internal surface of which acts as a template for the three‐dimensional (3D) clustering of water molecules. The structure and molecular dynamics of this material are characterised by single‐crystal X‐ray diffraction, thermogravimetric analysis, Raman (H/D isotopic substitution) spectroscopy, and ²H solid‐state (wide‐line and MAS) NMR spectroscopy. Material 1 is shown to be unusual because 1) few nanoporous materials exhibit a well‐organised 3D framework of water molecules, 2) it provides a unique opportunity to follow experimentally and to rationalise the deconstruction of a 3D water framework and 3) despite the fact that the hybrid framework is a supramolecular salt, the structure does not collapse after dehydration and the final material is crystalline.     

Polyoxometalate‐Based Entangled Coordination Networks Induced by an Extended Bis(triazole) Ligand

The introduction of an extended bridging bis(triazole) ligand, that is, 4,4′‐bis(1,2,4‐triazol‐1‐ ylmethyl)biphenyl (BBPTZ), into the hydrothermal reaction system containing transition metal ions and Keggin‐type polyoxometalates (POMs) led to the isolation of three new organic–inorganic hybrid entangled coordination networks, [Cu^I₂Cu^II(BBPTZ)₆][SiW₁₂O₄₀]?12 H₂O ( 1 ), [Ni(BBPTZ)₂(H₂O)][H₂SiW₁₂O₄₀]?11 H₂O ( 2 ), and [Ni₂(BBPTZ)₄(H₂O)₂][SiW₁₂O₄₀]?3 H₂O ( 3 ). All three compounds were characterized by elemental analysis, IR spectroscopy, TG analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Compound 1 contains a 2‐D POM‐based metal–organic layer entangled with 1‐D ladder‐like metal–organic chains. The adjacent 2‐D networks are parallel to each other, further stacking into a 3‐D supramolecular framework with 1‐D channels. Compound 2 exhibits a 1‐D cantilever‐type loop‐containing chain. The Keggin‐type POMs act as the cantilever groups, leading to the adjacent catilever‐type chains interwaving together to form a 3‐D supramolecular open framework with two types of channels. Compound 3 possesses a 3‐D open framework based on 2‐D metal–organic undulated layer and Keggin‐type POM clusters. Three sets of such frameworks further interpenetrate with each other to form an interesting three‐fold interpenetrating framework. The photocatalytic activities of compounds 1–3 for the decomposition of methylene blue (MB) under UV light have been investigated.     

Two Keggin Templated Supramolecular Compounds by Exerting the Chelate and Linking Dual Roles of the Ligand 2, 2′‐Biimidazole

Two new Keggin templated supramolecular compounds, [Zn₂(H₂biim)₅(SiM₁₂O₄₀)] · 4H₂O [M = W ( 1 ), Mo ( 2 )] (H₂biim = 2, 2′‐biimidazole), were synthesized under hydrothermal conditions by using the ligand 2, 2′‐biimidazole. They were characterized by single‐crystal X‐ray diffraction, elemental analyses, IR and photoluminescence spectroscopy as well as cyclic voltammetry. The two isostructural compounds are constructed by two discrete supramolecular moieties: the inorganic chains consist of Keggin anions and metal‐organic chains constructed by [Zn₂(H₂biim)₅]⁴⁺ subunits. In the dinuclear [Zn₂(H₂biim)₅]⁴⁺ subunit, the H₂biim ligands exhibit a dual role, chelating and linking. The metal‐organic chains further construct a 3D supramolecular framework with channels, in which the Keggin‐based inorganic chains are accommodated. The electrochemical behaviors of compounds 1 and 2 bulk‐modified carbon paste electrodes ( 1 ‐CPE, 2 ‐CPE) were studied.     

Hydrothermal Syntheses, Crystal Structure and Thermal Behavior of [(CH_3)_2NH_2]_2[B_5O_6(OH)_4]_2·[HCON(CH_3)_2] and [NH_3CH_2CH_2NH_3]_2·[B_(14)O_(20)(OH)_6]

Two novel organic base templated nonmetal borates [(CH₃)₂NH₂]₂[B₅O₆(OH)₄]₂·[HCON(CH₃)₂] ( ? ) and [NH₃CH₂CH₂NH₃]₂[B₁₄O₂₀(OH)₆] ( II ) have been synthesized under hydrothermal conditions, and characterized by elemental analyses, FT‐IR spectroscopy, X‐ray diffraction, and TG‐DTA. Their crystal structures were determined from single crystal X‐ray diffraction. The crystal structure of compound I is characterized by forming a 3D supramolecular structure with large channels along axes b and c through O? H···O hydrogen‐bonding among the [B₅O₆(OH)₄]^? anions. The crystal structure of compound II is characterized by forming a 3D supramolecular structure with large channels along axis a and direction [111] through O? H···O hydrogen‐bonding among the [B₁₄O₂₀(OH)₆]^4? anions. The templating organic amine cations in I and II are both obtained through in situ hydrothermal reactions, and are both located in the channels of the 3D supramolecular structure, respectively. Their thermal behavior has been also investigated.     

A Novel Inorganic Clathrate Generated through Arene‐Arene Interactions

The direct mixing of CoCl₂, sodium 2,6‐pyridinedicarboxylate (Na₂(2,6‐pda)), KSCN, and 1,2‐bis(4‐pyridyl)ethane (bpye) in water at the ambient temperature afforded purple crystals readily. The crystal structure, as determined by X‐ray diffraction crystallography, consists of discrete inorganic [Co₂(η³‐2,6‐pda)₂(μ‐SCN)₂(H₂O)₂] and organic bpye molecules. Adjacent dicobalt molecules are connected via intermolecular hydrogen bonds, to form one‐dimensional hydrophobic channels in the solid state, which serve as a host framework to incarcerate bpye guests inside. Every organic molecule attaches to four adjacent inorganic species via arene‐arene interactions. The facile approach in assembling the dicobalt and bpye molecules together into an inorganic clathrate is demonstrated.     

Adsorption behaviour of a CdII–triazole MOF for butan‐2‐one in a single‐crystal‐to‐single‐crystal (SCSC) fashion: the role of hydrogen bonding and C—H…π interactions

The adsorption behaviour of the Cd^II–MOF {[Cd(L)₂(ClO₄)₂]·H₂O ( 1 ), where L is 4‐amino‐3,5‐bis[3‐(pyridin‐4‐yl)phenyl]‐1,2,4‐triazole, for butan‐2‐one was investigated in a single‐crystal‐to‐single‐crystal (SCSC) fashion. A new host–guest system that encapsulated butan‐2‐one molecules, namely poly[[bis{μ₃‐4‐amino‐3,5‐bis[3‐(pyridin‐4‐yl)phenyl]‐1,2,4‐triazole}cadmium(II)] bis(perchlorate) butanone sesquisolvate], {[Cd(C₂₄H₁₈N₆)₂](ClO₄)₂·1.5C₄H₈O}_n, denoted C₄H₈O@Cd‐MOF ( 2 ), was obtained via an SCSC transformation. MOF 2 crystallizes in the tetragonal space group P4₃2₁2. The specific binding sites for butan‐2‐one in the host were determined by single‐crystal X‐ray diffraction studies. N—H…O and C—H…O hydrogen‐bonding interactions and C—H…π interactions between the framework, ClO₄^? anions and guest molecules co‐operatively bind 1.5 butan‐2‐one molecules within the channels. The adsorption behaviour was further evidenced by ¹H NMR, IR, TGA and powder X‐ray diffraction experiments, which are consistent with the single‐crystal X‐ray analysis. A ¹H NMR experiment demonstrates that the supramolecular interactions between the framework, ClO₄^? anions and guest molecules in MOF 2 lead to a high butan‐2‐one uptake in the channel.     

Highly Selective Water Adsorption in a Lanthanum Metal–Organic Framework

We present a new metal–organic framework (MOF) built from lanthanum and pyrazine‐2,5‐dicarboxylate (pyzdc) ions. This MOF, [La(pyzdc)_1.5(H₂O)₂] ? 2 H₂O, is microporous, with 1D channels that easily accommodate water molecules. Its framework is highly robust to dehydration/hydration cycles. Unusually for a MOF, it also features a high hydrothermal stability. This makes it an ideal candidate for air drying as well as for separating water/alcohol mixtures. The ability of the activated MOF to adsorb water selectively was evaluated by means of thermogravimetric analysis, powder and single‐crystal X‐ray diffraction and adsorption studies, indicating a maximum uptake of 1.2 mmol g^?1 MOF. These results are in agreement with the microporous structure, which permits only water molecules to enter the channels (alcohols, including methanol, are simply too large). Transient breakthrough simulations using water/methanol mixtures confirm that such mixtures can be separated cleanly using this new MOF.     

Water de/adsorption associated with single‐crystal‐to‐single‐crystal structural transformation of a series of two‐dimensional metal–organic frameworks, [M(bipy)(C4O4)(H2O)2]·3H2O (M = Mn (1), Fe (2), and Zn (3), and bipy=4,4′‐bipyridine)

An assembly of three metal coordination polymers (CPs), [M(bipy)(C₄O₄)(H₂O)₂]·3H₂O (M = Mn ( 1 ), Fe ( 2 ), Zn ( 3 ), and bipy = 4,4′‐bipyridine, C₄O₄^2? (squarate) = dianion of H₂C₄O₄ (squaric acid)), was synthesized and structurally characterized. Single‐crystal X‐ray structural determination reveals that compounds 1 – 3 are iso‐structural, in which the M(II) ions are six‐coordinate in a distorted octahedral geometry. C₄O₄^2? and bipy both act as bridging ligands with bis‐monodentate coordination mode connecting the M(II) ions to form a two‐dimensional (2D) layered metal–organic framework (MOF). Adjacent 2D layers are then arranged in parallel and interpenetrated manners to construct their three‐dimensional (3D) supramolecular architecture. Compounds 1 , 2 , and 3 undergo two‐step dehydration processes with the first and second weight losses of 14.1 and 8.6% for 1 , of 12.1 and 7.5% for 2, and of 11.2 and 8.1% for 3 , respectively, corresponding to the weight losses of the three guest water molecules and the two coordinated water molecules, and all exhibit reversible sponge‐like water de/adsorption properties during de/rehydration processes for guest water molecules as per cyclic thermogravimetric analysis (TGA). The single‐crystal‐to‐single‐crystal (SCSC) structural transformation during the reversible de/rehydration processes of three guest water molecules was identified and monitored using exhaustive single‐crystal and powder X‐ray diffraction measurements.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Synthesis and Crystal Structure of an Unprecedented Supramolecular Complex [Co(μ2-ClO4)2(H2O)2]•2MA

利用水热法合成了一个结构新颖的超分子化合物[Co(μ2-ClO4)2(H2O)2]·2MA (1),晶体结构表明化合物1是靠氢键和p - p相互作用形成的独特的有机-无机杂化型三维超分子配合物。结构中存在两种不同的超分子构件：a)一维无机链通过氢键形成二维(4,4)拓扑网状构筑单元[Co(μ2-ClO4)2(H2O)2];b)三嗪环之间靠p - p相互作用形成的zigzag链状构筑单元。二者之间通过丰富的氢键和p-p相互作用最终形成了一个三维超分子结构。     

A Polyoxometalate‐Encapsulating Cationic Metal–Organic Framework as a Heterogeneous Catalyst for Desulfurization

A new cationic triazole‐based metal–organic framework encapsulating Keggin‐type polyoxometalates, with the molecular formula [Co(BBPTZ)₃][HPMo₁₂O₄₀]?24 H₂O [compound 1 ; BBPTZ=4,4′‐bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The structure of compound 1 contains a non‐interpenetrated 3D CdSO₄ (cds)‐type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin‐type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size‐selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system.     

Two Robust Porous Metal–Organic Frameworks Sustained by Distinct Catenation: Selective Gas Sorption and Single‐Crystal‐to‐Single‐Crystal Guest Exchange

Assembly of copper(I) halide with a new tripodal ligand, benzene‐1,3,5‐triyl triisonicotinate (BTTP4), afforded two porous metal–organic frameworks, [Cu₂I₂(BTTP4)]?2 CH₃CN ( 1? 2 CH₃CN) and [CuBr(BTTP4)]?(CH₃CN ? CHCl₃ ? H₂O) ( 2? solvents), which have been characterized by IR spectroscopy, thermogravimetry (TG), single‐crystal, and powder X‐ray diffraction (PXRD) methods. Compound 1.CH3CN is a polycatenated 3D framework that consists of 2D (6,3) networks through inclined catenation, whereas 2 is a doubly interpenetrated 3D framework possessing the ThSi₂‐type ( ths ) (10,3)‐b topology. Both frameworks contain 1D channels of effective sizes 9×12 and 10×10 Ų, which amounts to 43 and 40 % space volume accessible for solvent molecules, respectively. The TG and variable‐temperature PXRD studies indicated that the frameworks can be completely evacuated while retaining the permanent porosity, which was further verified by measurement of the desolvated complex [Cu₂I₂(BTTP4)] ( 1′ ). The subsequent guest‐exchange study on the solvent‐free framework revealed that various solvent molecules can be adsorbed through a single‐crystal‐to‐single‐crystal manner, thus giving rise to the guest‐captured structures [Cu₂I₂(BTTP4)]?C₆H₆ ( 1.benzene ), [Cu₂I₂(BTTP4)]?2 C₇H₈ ( 1.2toluene ), and [Cu₂I₂(BTTP4)]?2 C₈H₁₀ ( 1.2ethyl benzene ). The gas‐adsorption investigation disclosed that two kinds of frameworks exhibited comparable CO₂ storage capacity (86–111 mL g^?1 at 1 atm) but nearly none for N₂ and H₂, thereby implying its separation ability of CO₂ over N₂ and H₂. The vapor‐adsorption study revealed the preferential inclusion of aromatic guests over nonaromatic solvents by the empty framework, which is indicative of selectivity toward benzene over cyclohexane.     

Syntheses,crystal structures and blue emission of three zinc(II) coordination polymers with a 4,4′‐dicarboxybiphenyl sulfone ligand

Three novel zinc complexes [Zn(dbsf)(H₂O)₂] ( 1 ), [Zn(dbsf)(2,2′‐bpy)(H₂O)]·(i‐C₃H₇OH) ( 2 ) and [Zn(dbsf)(DMF)] ( 3 ) (H₂dbsf = 4,4′‐dicarboxybiphenyl sulfone, 2,2′‐bpy = 2,2′‐bipyridine, i‐C₃H₇OH = iso‐propanol, DMF = N,N‐dimethylformamide) were first obtained and characterized by single crystal X‐ray crystallography. Although the results show that all the complexes 1–3 have one‐dimensional chains formed via coordination bonds, unique three‐dimensional supramolecular structures are formed due to different coordination modes and configuration of the dbsf^2? ligand, hydrogen bonds and π–π interactions. Iso‐propanol molecules are in open channels of 2 while larger empty channels are formed in 3 . As compared with emission band of the free H₂dbsf ligand, emission peaks of the complexes 1–3 are red‐shifted, and they show blue emission, which originates from enlarging conjugation upon coordination. Copyright © 2006 John Wiley & Sons, Ltd.     

Towards a New Family of Photoluminescent Organozinc 8‐Hydroxyquinolinates with a High Propensity to Form Noncovalent Porous Materials

We report on investigations of reactions of tBu₂Zn with 8‐hydroxyquinoline (q‐H) and the influence of water on the composition and structure of the final product. A new synthetic approach to photoluminescent zinc complexes with quinolinate ligands was developed that allowed the isolation of a series of structurally diverse and novel alkylzinc 8‐hydroxyquinolate complexes: the trinuclear alkylzinc aggregate [tBuZn(q)]₃ ( 1₃ ), the pentanuclear oxo cluster [(tBu)₃Zn₅(μ₄‐O)(q)₅] ( 2 ), and the tetranuclear hydroxo cluster [Zn(q)₂]₂[tBuZn(OH)]₂ ( 3 ). All compounds were characterized in solution by ¹H NMR, IR, UV/Vis, and photoluminescence (PL) spectroscopy, and in the solid state by X‐ray diffraction, TGA, and PL studies. Density functional theory calculations were also carried out for these new Zn^II complexes to rationalize their luminescence behavior. A detailed analysis of the supramolecular structures of 2 and 3 shows that the unique shape of the corresponding single molecules leads to the formation of extended 3D networks with 1D open channels. Varying the stoichiometry, shape, and supramolecular structure of the resulting complexes leads to changes in their spectroscopic properties. The close‐packed crystal structure of 1₃ shows a redshifted emission maximum in comparison to the porous crystal structure of 2 and the THF‐solvated structure of 3 .     

Synthesis and Characterization of a Novel Organic/Inorganic Hybrid Based on Octamolybdates and Benzimidazole Molecules [Hbenzimi]4 [(benzimi)2Mo8O26] · 2H2O (benzimi?=?benzimidazole)

A novel organic/inorganic compound [Hbenzimi]₄[(benzimi)₂Mo₈O₂₆] · 2H₂O (1) has been prepared hydrothermally and characterized by elemental analyses, i.r., x.p.s., t.g. and single crystal X-ray diffraction. The single crystal X-ray diffraction analysis reveals that compound (1) consists of the [Mo₈O₂₆]⁴⁻ cluster as the structural motif covalently linked by benzimidazole molecules and protonated benzimidazole molecules as charge compensation cations. It is interesting that the benzimidazole molecules were synthesized from 1,2-phenylenediamine and oxalic acid. The [Mo₈O₂₆]⁴⁻ polyoxoanions and organic ligands in compound (1) interact with each other via extensive hydrogen bonds to form a three-dimensional supramolecular framework.     

Synthesis and Structure Characterization of Metal‐organic Frameworks with a Triple Iron Helical Complex

Metal‐organic frameworks were achieved from triple metal helical iron complex [(Fe₂L₃)·(H₂O)₄] (L = bis[2‐hydroxybenzaldehyde]hydrazonate). The phenyl rings of the helical units contact the neighbors via π‐π and C‐H···π interactions to form two‐dimensional channeled frameworks in which four solvent water molecules are included in the channels of the structure. Thermogravimetric analyses reveal that the solvent water molecules can be evacuated from the pores without loss of the framework periodicity. The crystal lattice is thermally stable up to 339.9 °C, and water can be re‐included by putting the heated material in water.     

基于2,4′-二羧基二苯甲酮构筑的具有一维梯状链和一维隧道的三维超分子体系

采用水热法设计合成了两个新型三维超分子化合物H₂L·H₂O (1)和[Ag(bpy)₂]·HL·H₂O (2) (其中bpy=2,2'-联吡啶, H₂L=2,4′-二羧基二苯甲酮),晶体结构分析表明,它们均是通过氢键采用不同的连接方式拓展而成。其中,化合物1 是2,4′-二羧基二苯甲酮和水分子通过O–H···O氢键形成的一维梯状链扩展构筑的三维超分子体系;化合物2 则是2,4′-二羧基二苯甲酮和水分子通过两种氢键形成含有一维隧道的三维超分子体系。有趣的是,[Ag(bpy)₂]⁺ 阳离子通过π–π 堆积和弱的Ag···Ag相互作用连在一起,进而以客体形式填充其中。荧光性质研究表明,由于存在bpy的螯合与堆积效应,化合物2相比配体和化合物1,其荧光发射峰发生红移。     

Supramolecular Architectures with Open Frameworks Constructed by Transitional Metal Ions,Linear Dicarboxylic Acid,and 2,2′‐Bipyridine

Four new transitional metal supramolecular architectures, [Zn(cca)(2,2′‐bpy)]_n · n(2,2′‐bpy) ( 1 ), [Cu(cca)(2,2′‐bpy)]_n ( 2 ), [Zn(bpdc)(2,2′‐bpy)(H₂O)]_n · 0.5nDMF · 1.5nH₂O ( 3 ), and [Co(bpdc)(2,2′‐bpy)(H₂O)]_n · nH₂O ( 4 ) (H₂cca = p‐carboxycinnamic acid; H₂bpdc = 4,4′‐biphenyldicarboxylic acid; 2,2′‐bpy = 2,2′‐bipyridine) were synthesized by hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. Although the metal ions in these four compounds are bridged by linear dicarboxylic acid into 1D infinite chains, there are different π–π stacking interactions between the chains, which results in the formation of different 3D supramolecular networks. Compound 1 is of a 3D open‐framework with free 2,2′‐bpy molecules in the channels, whereas compound 2 is of a complicated 3D supramolecular network. Compounds 3 and 4 are isostructural. Both compounds have open‐frameworks.     

Water‐Soluble Three‐Dimensional Polymers: Non‐Covalent and Covalent Synthesis and Functions†

Water‐soluble three‐dimensional (3D) polymers are structurally ideal for the construction of ordered porous materials for in‐situ and tunable loading and release of guests. For many years, studies on ordered porous materials have been confined to crystalline solids. Since 2014, self‐assembly has been developed as a robust strategy for the preparation of water‐soluble 3D polymers that possess defined and intrinsic porosity. Through the encapsulation of cucurbit[8]uril for aromatic dimers, ordered diamondoid supramolecular organic frameworks can be assembled from tetrahedral monomers. With [Ru(bipy)₃]²⁺‐derived octahedral complexes as precursors, cubic supramolecular metal‐organic frameworks have been assembled. One supramolecular organic framework has also been utilized to prepare the first homogeneous covalent organic framework through the [2+2] alkene cycloaddition, whereas the quantitative formation of the hydrazone bonds can be utilized to synthesize flexible porous organic frameworks. The new water‐soluble ordered and flexible polymeric frameworks are able to include drugs and biomacromolecules to accomplish in situ loading and intracellular delivery and to enrich photosensitizers and catalysts to enhance discrete visible light‐induced reactions. This review highlights the advances.     

Synthesis,Crystal Structure,and Characterization of a Novel Metallo‐Organically‐Templated Pentaborate with Mixed Ligands

A novel metallo‐organically templated pentaborate with layered framework, [Cd(TETA)(C₂H₃O₂)][B₅O₆(OH)₄] ( 1 ) (TETA = triethylenetramine), was synthesized under mild solvothermal conditions. The structure was determined by single‐crystal X‐ray diffraction and further characterized by FT‐IR spectroscopy, elemental analysis, thermogravimetric analysis, and photoluminescence spectroscopy. The structure consists of an isolated polyborate anion [B₅O₆(OH)₄]^– and the cadmium complex cation of [Cd(TETA)(C₂H₃O₂)]⁺, which contains both organic amine and organic acid ligands. The [B₅O₆(OH)₄]^– units are connected together by hydrogen bonds, and a 2D sheet‐like framework with rectangle‐like 12‐membered boron rings are formed. The [Cd(TETA)(C₂H₃O₂)]⁺ complex cations are located in the free space between the layers and connect the adjacent borate layers through hydrogen bonds to form a three‐dimensional supramolecular network. The luminescent properties of the compound were studied for the first time in the series of metallo‐organically‐templated pentaborates, and a blue luminescence occurs with an emission maximum at 468 nm upon excitation at 397 nm.