Search

Colon cancer is the third most common malignancy and the fourth most prevalent cause of death worldwide. Unfortunately, current cancer treatment approaches suffer from low specificity toward colon ...

Irradiation of single crystals of a ladder-like coordination chain with 365 nm UV light induces a regiospecific photochemical [2 + 2] cycloaddition reaction of each pair of adjacent diolefinic ligands from neighbouring crystallographically equivalent chains and thus affords a two-dimensional (4,4)-connected coordination network through single-crystal to single-crystal transformation.

Development of T1/T2 dual-mode MRI contrast agents that can also treat cancer is an attractive prospect for personalized precision medicine. Unfortunately, conventional contrast agents can suffer from toxicity and lack any ability to treat cancer. An all-iron T1/T2 MR imaging agent with photothermal and drug delivery capability would overcome these issues. Here, an avocado-like Fe3+/Fe2O3 composed T1-T2 dual-mode contrast agent based on Fe-TA coordination network (CNMN) is developed. This material possesses suitable longitudinal and transverse relaxation coefficients. Moreover, the strong heat generation property of Fe-TA endows CNMN with the capability to act as a potent photothermal agent. Furthermore, CNMN can also act as an effective delivery platform for the chemotherapeutic drug doxorubicin (DOX) to achieve high effective chemo-photothermal combination therapy. The work demonstrates reliable T1-T2 MRI-guided chemo-photothermal therapy for safe and effective clinical application.

The Prussian blue (PB) based nanostructure is a mixed-valence coordination network with excellent biosafety, remarkable photothermal effect and multiple enzyme-mimicking behaviours. Compared with other nanomaterials, PB-based nanoparticles (NPs) exhibit several unparalleled advantages in biomedical applications. This review begins with the chemical composition and physicochemical properties of PB-based NPs. The tuning strategies of PB-based NPs and their biomedical properties are systemically demonstrated. Afterwards, the biomedical applications of PB-based NPs are comprehensively recounted, mainly focusing on treatment of tumors, bacterial infection and inflammatory diseases. Finally, the challenges and future prospects of PB-based NPs and their application in disease treatment are discussed.

Chemical science 11(34), 9067 - 9071 (2020). doi:10.1039/D0SC03437A, Despite the proven ability to form supramolecular assemblies via coordination to copper halides, organometallic building blocks based on four-membered cyclo-P4 ligands find only very rare application in supramolecular chemistry. To date, only three types of supramolecular aggregates were obtained based on the polyphosphorus end-deck complexes Cp$^R$Ta(CO)$_2$($η^4$-P$_4$) (1a: CpR = Cp′′; 1b: Cp$^R$ = Cp′′′), with none of them, however, possessing a guest-accessible void. To achieve this target, the use of silver salts of the weakly coordinating anion SbF$_6^−$ was investigated as to their self-assembly in the absence and in the presence of the template molecule P$_3$Se$_4$. The two-component self-assembly of the building block 1a and the coinage-metal salt AgSbF$_6$ leads to the formation of 1D or 3D coordination polymers. However, when the template-driven self-assembly was attempted in the presence of an aliphatic dinitrile, the unprecedented barrel-like supramolecular host–guest assembly P$_3$Se$_4$@[{(Cp′′Ta(CO)$_2$($η^4$-P$_4$))Ag}$_8$]$^{8+}$ of 2.49 nm in size was formed. Moreover, cyclo-P$_4$-based supramolecules are connected in a 2D coordination network by dinitrile linkers. The obtained compounds were characterised by mass-spectrometry, $^1$H and $^{31}$P NMR spectroscopy and X-ray structure analysis., Published by RSC, Cambridge

International audience; Two novel hetero-and homoleptic Au(III) complexes based on a dithiolene ligand bearing two 4-thiopyridyl groups have been designed, synthesized and characterized in solution and in the crystalline state. These species have been employed as metalloligands, or metallatectons, for the elaboration of heterometallic coordination polymers upon assembly with M(NCS)2 salts (M = Mn, Co, Cd) and Co(N(CN)2)2 respectively. Upon combination of the neutral heteroleptic complex comprising a cyclometallating benzo[h]quinoline fragment and the mononuclear Mn(NCS)2 and Co(NCS)2 nodes, one-dimensional coordination networks were obtained. They feature pendant heteroleptic complexes that stack centrosymmetrically in the crystalline state leading to an interdigitated system, analogous to what has been reported with the parent EDT-TTF derivative. With Cd(NCS)2, the inorganic moieties form a two-dimensional ruffled layer with bridging thiocyanate anions, while the Au(III) complexes occupy the remaining apical positions of the Cd(II) centers. This leads to a stacking of the heteroleptic species. With the homoleptic complex, monoanionic analogue of a symmetrical TTF, a two-dimensional coordination network was obtained by combination with Co(N(CN)2)2, featuring one dimensional [Co(N(CN)2)]α chains. These networks have been characterized in the crystalline state by X-ray diffraction and represent, to the best of our knowledge, the first heterometallic coordination polymers based on Au(III) dithiolene complexes and transition metal cations.

The tetratopic 1,4-bis(2-phenylethoxy)-2,5-bis(3,2′:6′,3′′-terpyridin-4′-yl)benzene (1) and 1,4-bis(3- phenylpropoxy)-2,5-bis(3,2′:6′,3′′-terpyridin-4′-yl)benzene (2) ligands have been prepared and fully characterised. Combination of ligand1or2and [M(hfacac)2]·xH2O (M = Cu,x= 1; M = Zn,x= 2) under conditions of crystal growth by layering led to the formation of [Cu2(hfacac)4(1)]n·3.6n(1,2-Cl2C6- H4)·2nCHCl3, [Zn2(hfacac)4(1)]n·nMeC6H5·1.8nCHCl3, [Cu2(hfacac)4(2)]n·nMeC6H5·2nH2O, [Cu2(hfacac)4(2)]n·2.8nC6H5Cl and [Cu2(hfacac)4(2)]n·2n(1,2-Cl2C6H4)·0.4nCHCl3·0.5nH2O. For each compound, single-crystal X-ray analysis revealed the assembly of a planar (4,4)-net in which the tetratopic ligands1or2define the nodes. The metal centres link two different bis(3,2′:6′,3′′-tpy) ligandsviathe outer pyridine rings; whereas copper(II) has N-donors in atrans-arrangement, zinc(II) has them incis. This difference between the copper(II) and zinc(II) coordination polymers modifies the architecture of the assembly without changing the underlying (4,4)-network

The coordination network compounds (CNCs) {[M(Ltriaz)](DMF)}n (M is Zn or Co, H2Ltriaz is 5-(4H-1,2,4- triazol-4-yl)benzene-1,3-dicarboxylic acid, and DMF is N,N-dimethylformamide) with crystallographically identifiable disorder were solvothermally synthesized. The effects of structural disorder on the pore size and stability of T-shaped triazolyl-based CNCs were determined for the first time. In contrast to isostructurally ordered ones, the pore sizes of Zn-CNC and Co-CNC changed, and the stability of Zn-CNC was improved.

Metal-coordinated frameworks derived from small peptidic ligands have received much attention thanks to peptides' vast structural and functional diversity. Various peptides with partial conformational preferences have been used to build metal-peptide frameworks, however, the use of conformationally constrained β-peptide foldamers has not been explored yet. Herein we report the first metal-coordination-mediated assembly of β-peptide foldamers with 12-helical folding propensity. The coordination of Ag+ to the terminal pyridyl moieties afforded a set of metal-peptide frameworks with unique entangled topologies. Interestingly, formation of the network structures was accompanied by notable conformational distortions of the foldamer ligands. As the first demonstration of new metal-peptide frameworks built from modular β-peptide foldamers, we anticipate that this work will be an important benchmark for further structural evolution and mechanistic investigation.

The structure of catena-[tris­(μ4-benzene-1,4-di­carboxyl­ato)-tetra­kis­(μ1– di­methyl­formamide-κ1 O)-trinickel(II)], C36H40N4Ni3O16, has been determined in the monoclinic P21/n space group. The compound has a two-dimensional coordination network structure and it is of inter­est with respect to lithium-ion battery applications. Hirshfeld surface analysis was performed to characterize inter­planar inter­actions. The structure exhibits disorder of coordinated solvent mol­ecules., The crystal structure of the title compound, [Ni3(C8H4O4)3(C3H7NO)4], is a two-dimensional coordination network formed by trinuclear linear Ni3(tp)3(DMF)4 units (tp = terephthalate = benzene-1,4-di­carboxyl­ate and DMF = di­methyl­formamide) displaying a characteristic coordination mode of acetate groups in polynuclear metal–organic compounds. Individual trinuclear units are connected through tp anions in a triangular network that forms layers. One of the DMF ligands points outwards and provides inter­actions with equivalent planes above and below, leaving the second ligand in a structural void much larger than the DMF mol­ecule, which shows positional disorder. Parallel planes are connected mainly through weak C—H⋯O, H⋯H and H⋯C inter­actions between DMF mol­ecules, as shown by Hirshfeld surface analysis.

The tunable growth of metal-organic materials has implications for engineering particles and surfaces for diverse applications. Specifically, controlling the self-assembly of metal-phenolic networks (MPNs), an emerging class of metal-organic materials, is challenging, as previous studies suggest that growth often terminates through kinetic trapping. Herein, kinetic strategies were used to temporally and spatially control MPN growth by promoting self-correction of the coordinating building blocks through oxidation-mediated MPN assembly. The formation and growth mechanisms were investigated and used to engineer films with microporous structures and continuous gradients. Moreover, reactive oxygen species generated by ultrasonication expedite oxidation and result in faster (ca. 30 times) film growth than that achieved by other MPN assembly methods. This study expands our understanding of metal-phenolic chemistry towards engineering metal-phenolic materials for various applications.

peer-reviewed The selective separation of ethanol/acetonitrile by porous materials has rarely been observed owing to their similar physicochemical properties. In this work, we report a new coordination network, [Cu2(4-pmntd)2(opd)2](4-pmntd = N,N′-bis(4- pyridymethy)naphthalene diimide, opd = disodium 1,2-benzenedicarboxylate), which exhibits selective separation of ethanol over acetonitrile. The weak coordination bonds formed by unsaturated Cu2+ sites and hydroxyl groups are the key to such performance

Coordination polymers (CPs) and coordination network solids such as metal–organic frameworks (MOFs) have gained increasing interest during recent years due to their unique properties and potential applications. Preparing 3D printed structures using CP would provide many advantages towards utilization in fields such as catalysis and sensing. So far, functional 3D structures were printed mostly by dispersing pre-synthesized particles of CPs and MOFs within a polymerizable carrier. This resulted in a CP active material dispersed within a 3D polymeric object, which may obstruct or impede the intrinsic properties of the CP. Here, we present a new concept for obtaining 3D free-standing objects solely composed of CP material, starting from coordination metal complexes as the monomeric building blocks, and utilizing the 3D printer itself as a tool to in situ synthesize a coordination polymer during printing, and to shape it into a 3D object, simultaneously. To demonstrate this, a 3D-shaped nickel tetra-acrylamide monomeric complex composed solely of the CP without a binder was successfully prepared using our direct print-and-form approach. We expect that this work will open new directions and unlimited potential in additive manufacturing and utilization of CPs. National Research Foundation (NRF) Published version This research was supported by the grants from the National Research Foundation, Prime Minister's Office, Singapore under its Campus of Research Excellence and Technological Enterprise (CREATE) Programme, Nanomaterials for Energy and Water-Energy Nexus, and by the Hebrew university fund for PhD students.

Reversible single-crystal-to-single-crystal photocyclization–cycloreversion reaction of a stilbene-based coordination network exhibits a conspicuous fluorescence change. The controllable fluorescence and high fatigue resistance feature of this bistable material make it a single-crystalline device for applications in rewritable optical memory storage systems.

The first 4,2′:6′,4′′-terpyridine (4,2′:6′,4′′-tpy) containing coordination polymer was reported over 20 years ago and in the last decade, there has been increased interest in the use of ditopic 4,2′:6′,4′′-tpy ligands as linkers in coordination polymers and 2D-networks. Functionalization in the 4′-position of 4,2′:6′,4′′-tpy is synthetically straightforward, giving access to a large suite of building blocks. Less well explored is the coordination chemistry of 3,2′:6′,3′′-tpy ligands which exhibit greater conformational flexibility than 4,2′:6′,4′′-tpy. One approach to making the transition from 2D- to 3D-networks is to utilize tetratopic bis(4,2′:6′,4′′-tpy) and bis(3,2′:6′,3′′-tpy) ligands which act as 4-connecting nodes. In this highlight, we survey recent progress towards a better understanding of the design principles associated with the use of ditopic and tetratopic 4,2′:6′,4′′-tpy and 3,2′:6′,3′′-tpy containing ligands and their roles both as linkers and nodes in coordination assemblies.

peer-reviewed We report a 2-fold interpenetrated primitive cubic (pcu) network X-pcu-5-Zn, [Zn2(DMTDC)2(dpe)] (H2DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene), that exhibits reversible switching between an as-synthesized “open” phase, X-pcu-5-Zn-α, and two nonporous or “closed” polymorphs, X-pcu-5-Zn-β and X-pcu-5-Zn-γ. There are two unusual features of X-pcu-5-Zn. The first relates to its sorption properties, which reveal that the α form exhibits high CO2 uptake (ca. 255 cm3/g at 195 K) via reversible closed-to-open switching (type F-IV isotherm) of the type desirable for gas and vapor storage; there are only three other reports of porous materials that combine these two features. Second, we could only isolate the β form by activation of the CO2 loaded α form and it persists through multiple CO2 adsorption/desorption cycles. We are unaware of a new polymorph having been isolated in such a manner. That the observed phase changes of X-pcu-5-Zn-α occur in single-crystal-to-single-crystal fashion enabled structural characterization of the three forms; γ is a coordination isomer of α and β, both of which are based upon “paddlewheel” clusters. The full text of this article will not be available in ULIR until the embargo expires on the 05/11/2019

Two coordination polymers, {[Cd(L1)2(L2)] · 0.25H2O} n (I) and {[Cd(L1)(L3)H2O] · 2H2O} n (II) (L1 = 2-pyrimidineamidoxime, L2 = 4-sulfobenzoate dianion and L3 = 5-sulfosalicylate dianion), has been synthesized and structurally characterized by single-crystal X-ray diffraction (CIF files CCDC nos. 1565646 (I) and 1565728 (II)). Complex I crystallizes in monoclinic space group P21/n with a = 10.1462(3), b = 16.0152(5), c = 14.0349(5) A, β = 93.267(3)°, V = 2276.87(13) A3, C68H66N32O29S4Cd4, M = 2373.36, ρcalcd = 1.731 g/cm3, μ(MoKα) = 1.109 mm−1, F(000) = 1186, GOOF = 0.806, Z = 1, the final R1 = 0.0287 and wR2 = 0.0733 for I > 2σ(I). Complex II crystallizes in monoclinic space group P21 with a = 6.882(2), b = 17.138(2), c = 7.883(2) A, β = 103.83(3)°, V = 902.8(4) A3, C12H16N4O10SCd, M = 520.75, ρcalcd = 1.916 g/cm3, μ(MoKα) = 1.388 mm−1, F(000) = 520, GOOF = 1.047, Z = 2, the final R1 = 0.0739 and wR2 = 0.2041 for I > 2σ(I). Crystal structural analysis reveals that complex I possesses the corrugated 1D chain structure extending along the $$[\bar 101]$$ direction. However, complex II displays a 2D coordination network lying on the ab crystal plane, which can be simplified as a binodal 3-connected 63 topological network by considering Cd2+ ions and L3 ligands as 3-connected nodes. Their photoluminescent and thermal properties were also investigated.

The coordination polymer, [MnL0.5(H2O)(phen)] n (H4L = 1,1':4',1''-terphenyl-2',4,4'',5'-tetracarboxylic acid, phen = 1,10-phenanthroline), has been solvothermal synthesized and structurally characterized by single-crystal X-ray diffraction. Complex crystallizes in triclinic sp. gr. $$P\bar 1$$ with Z = 2. Two carboxylate oxygen atoms in the central phenyl rings from two μ $${u_{{6^ - }}}$$ L4– ligands doubly-bridge two Mn(II) ions to form the dinuclear $$M{n_2}{({O_{CO{O^ - }}})_2}$$ unit. Each dinuclear $$M{n_2}{({O_{CO{O^ - }}})_2}$$ unit links four L4– ligands and each L4–ligand bridges four dinuclear $$M{n_2}{({O_{CO{O^ - }}})_2}$$ units to generate a 2D coordination network, which can be rationalized as a binodal (4,4) topological network by considering the dinuclear $$M{n_2}{({O_{CO{O^ - }}})_2}$$ units and L4– ligands as 4-connected nodes.

The multistate redox-active/multi-interactive ligand 5,5',8,8'-tetra(4-pyridyl)-2,2'-(1,4-phenylene)bis-1H-perimidine (H2 TPP) was designed and synthesized. H2 TPP undergoes four one-electron oxidation steps, and was used for the preparation of a multistate redox-active coordination network in a solid-liquid interface reaction using molten Cd2+ salts. The multiple redox states of H2 TPP were confirmed spectroscopically by stepwise four-electron oxidation. Spectroscopic analysis indicated that the mixed-valence states of the ligand are class II on the UV/Vis/NIR timescale and borderline class II/class III on the ESR timescale.

Four new MnII- and CoII-containing magnetic coordination polymers, [{Mn(Br-isa)(bpe)·1/2H2O}n (1), {Co(Br-isa)(bpe)1.5·1/2H2O}n (2), [{Mn(Br-isa)(4-bpmh)}4·6H2O]n (3), and [{Co(Br-isa)(4-bpmh)}2·21/2H2O]n (4)] [isa = isophthalic acid, bpe = 1,2-bis-(4-pyridyl)ethylene and 4-bpmh = N,N′-bispyridine-4-yl-methylene-hydrazine], have been synthesized at room temperature, using 5-bromo isophthalic acid (Br-H2isa) and two different N-donating ancillary ligands. The complexes have been characterized by single-crystal X-ray diffraction and other physicochemical techniques. Structure determination reveals two-dimensional (2D) coordination network architectures for all the complexes. In 1, 3, and 4, MnII and CoII dinuclear units are connected via Br-H2isa ligands to form infinite 1D chains. The ancillary N,N′-donor spacer ligands interconnect the 1D chains into 2D coordination layers. Complex 2, on the other hand, can be viewed as being composed of cationic [{Co(bpe)}4]8+ square units that are joined by anionic Br-i...

The design of redox-active metal-organic frameworks and coordination networks (CNs), which exhibit metal- and/or ligand-centered redox activity, has recently received increased attention. In this study, the redox-active metalloligand (RML) [Me4N]3fac-[CrIII(mp)3] (1) (mp = 2-mercaptophenolato) was synthesized and characterized by single-crystal X-ray diffraction analysis, before its reversible ligand-centered one-electron oxidation was examined by cyclic voltammetry and spectroelectrochemical measurements. As complex 1 contains OS coordination sites in three directions, complexation with K+ ions led to the formation of a two-dimensional honeycomb sheet-structured [K3fac-{CrIII(mp)3}(H2O)6]n (2·6H2O), which is the first example of a redox-active CN constructed from a RML with o-disubstituted benzene ligands. Herein, we unambiguously demonstrate the ligand-centered redox activity of the RML, which is incorporated in the redox-active CN 2·6H2O in the solid state.

Two coordination polymers, 1 and 2 were developed utilizing the favorable hexacoordinated zinc(II) center in porphyrins. Single crystal X-ray structure analysis revealed that 1 forms one dimensional array whereas 2 display three dimensional network structures. Scanning tunnelling microscopic studies have shown that compounds 1 and 2 can tunnel the electric current through the crystal lattice indicating the conducting behavior of these solid crystals. The self-assembled solid crystal 2 has shown uniform conductance whereas 1 does not. The thermal stability of these crystals were determined by TGA analysis and found to be stable up to a higher temperature of 400°C. A temperature dependent current–voltage analysis were also performed and the results indicate that the conductivity of crystals 1 and 2increases with increase in temperature. It is found that the temperature coefficient of resistance ([Formula: see text] at 100°C for 1 and 2 as -0.009 and 0.017 K[Formula: see text].

The single-crystal to single-crystal (SC–SC) transformation from a 1D coordination chain to a 3D coordination network, which is triggered by both solvent and anion exchanges, has been revealed to suffer from a tandem mechanism as proved by isolation of the intermediate state. The resulting porous crystalline material shows a high efficiency for the capture of dichromates (207 mg g−1) via the SC–SC anion-exchange.

A multistate redox-active coordination network was prepared by stepwise synthesis via mechanochemical reaction to overcome the low solubility of ligands. Solid-state grinding between sparingly solu...

The synthesis and characterization of 4′-(4-methoxyphenyl)-3,2′:6′,3″-terpyridine (2) (IUPAC PIN 24-(4-methoxyphenyl)-12,22:26,32-terpyridine) are described, and its coordination behaviour with cobalt(II) thiocyanate has been investigated. In a series of experiments, crystals were grown at room temperature by layering a MeOH solution of Co(NCS)2 over a CHCl3 solution of 2 using 1:1, 1:2 or 2:1 molar ratios of metal salt-to-ligand. Crystals harvested within 2–3 weeks proved to be the 1D-coordination polymer [Co(2)(NCS)2(MeOH)2]n and powder X-ray diffraction (PXRD) confirmed that the crystals selected for single-crystal X-ray diffraction were representative of the bulk samples. Longer crystallization times with a Co(NCS)2 to 2 molar ratio of 1:1 yielded crystals of [Co(2)(NCS)2(MeOH)2]n (1D-chain) and the pseudopolymorphs [{Co(2)2(NCS)2}·3MeOH]n and [{Co(2)2(NCS)2}·2.2CHCl3]n ((4,4)-nets), each type of crystal originating from a different zone in the crystallization tube. PXRD for this last experiment confirmed that the dominant product in the bulk sample was the 1D-coordination polymer.

We overview the coordination chemistry of ditopic and tetratopic ligands with 4,2':6',4''-terpyridine metal-binding domains and illustrate the adaptability of these divergent ligands as building blocks in 2D- and 3D-coordination networks. The ditopic ligands we discuss are limited to roles as linkers in coordination assemblies, while the tetratopic ligands have the potential to be 4-connecting nodes. Both di- and tetratopic ligands are equipped with functionalities, typically alkyloxy chains, the nature of which has a profound effect upon the coordination assembly. Combinations of 4-connecting ligand nodes with metal-linkers lead to both 2D- and 3D-networks, while combinations of 4-connecting metal and ligand nodes give 3D-architectures. We also demonstrate constraint of the coordination assembly to 2-dimensions by depositing ditopic 4,2':6',4"-terpyridine ligands onto Au(111) or Cu(111) platforms with Cu adatoms in the former case; highly ordered ladder assemblies result which are independent of solvent molecules or anions.

peer-reviewed Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu‐topology MOF, X‐pcu‐5‐Zn, have been prepared: X‐pcu‐6‐Zn, 6=1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn, 7=1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn, 8=4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N2, CO2, C2H2, and C2H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.

The single crystal X-ray structure determination of {[Cu(tpt)(o-phthalate)]·31/3(C2H2Cl4)}n (tpt = 2,4,6-tri-4-pyridyl-1,3,5-triazine, C2H2Cl4 = 1,1,2,2-tetrachloroethane = TCE) shows a 3D network in which CuII centres are linked by 3-connecting tpt ligands with the topology of a 12,3 net. CuII centres are further linked by o-phthalate dianions. The copper coordination geometry is square pyramidal, with o-phthalate oxygen donors trans to each other in the basal plane and the remaining positions taken by the pyridines of three linking tpt units. The solvent accessible void space is ∼65 %. The pale blue-green crystalline desolvate, obtained by heating to 200°C or washing the TCE solvate with acetone is formulated as [Cu(tpt)(o-phthalate)]n. Powder X-ray diffraction and electron paramagnetic resonance spectroscopy show that the crystal structure and the CuII geometry changes upon desolvation. The crystalline desolvated phase sorbs two equivalents of ammonia per copper ion. The adduct, mauve [Cu(tpt)(o-phthalate)(NH3)2]n, shows reasonable crystallinity and is stable up to ∼150°C under ambient conditions before the reversible desorption (minimum 10 cycles) of the guest ammonia. The colour change and high desorption temperature, along with changes in g values, is suggestive of chemisorption in two steps with Cu-ammine bonding in the loaded phase.

Catassembly is a new concept in molecular assembly that is analogous to catalysis in chemical synthesis. However, for most molecular-assembled processes, the catassembler contributions are rather inconspicuous due to the low activation barriers. As a result, few systems dealing with the catassembly are available until now. In this paper, we report that naphthalene diimide coordination networks are formed under the catassembly of lone-pair-bearing catassemblers (e.g., N,N-dimethylacetamide, N-methylpyrrolidin-2-one). During such molecular assembly, a stable transition state between the electron-deficient naphthalene diimide tectons and catassemblers via the less common lone pair-π interactions was observed, which is supposed to play the key role in the enhancement of coordination abilities of organic tectons and thus formation of the final coordination networks.

A comparative investigation of the coordination behaviour of the regio-isomers (o-L and p-L) of the tribenzo-O2S2-macrocycle (L) is reported. On silver(I) complexation, the macrocycle incorporating an o-xylyl group (o-L) yields a discrete endo/exocyclic tetranuclear bis(macrocycle) complex. On the other hand, the corresponding p-xylyl analogue (p-L) gives a 2D square-grid coordination network via exocyclic coordination.

Heating of a pink two-dimensional Co(II) coordination network {[Co2(μ2-OH2)(bdc)2(S-nia)2(H2O)(dmf)]·2(dmf)·(H2O)}n (1) built from 1,4-benzenedicarboxylic acid (H2bdc) residues and thionicotinamide (S-nia) ligands initiates a single-crystal-to-single-crystal transition accompanied by removal of both coordinated and co-crystallized solvents. In the dry blue form, [Co(bdc)(S-nia)]n (dry_1), the Co(II) centers changed from an octahedral to a square pyramidal configuration.

Upon combining enantiopure bis-4-pyridylphenyl-substituted cyclotetrapeptides with HgCl2 and CdCl2, homochiral 1D zigzag coordination polymers were obtained, while the use of a bis-4-pyridyl-substituted cyclotetrapeptide with HgCl2 led to the formation of a different type of 1D coordination network.

International audience; Depending on the nature of the anion (NO3-or BF4-) and stoichiometry, combinations, under self-assembly conditions, of the [1.1.1.1]metacyclophane 2 adopting a blocked 1,3-alternate conformation and bearing four cyanomethylene groups, with silver cations, lead either to the formation of a 1D coordination network or a discrete binuclear metallomacrocycle.

In the two dimensional network [Fe(ebbtr)2(CH3CN)2](ClO4)2·4CH3CN a sequence of LS → HS → LS → HS transitions occurs as the exclusive result of the change in temperature. This property results from the extraordinary flexibility/elasticity manifested in the hierarchical arrangement of structural events involving the reorientation of coordinated/noncoordinated molecules as well as with the deformation and the mutual shift of the polymeric units.

Although the cyclo-P6 complex [(Cp*Mo)2(μ,η6:η6-P6)] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the “naked” cations Cu+, Ag+, and Tl+. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2]+ complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M+ cations. The choice of solvent enabled control over the reaction outcome for Cu+, as proved by powder XRD and supported by DFT calculations. The reaction with Tl+ affords a layered two-dimensional coordination network in the solid state.

Reactions of the flexible N,N′-di(3-pyridyl)suberoamide (L) with Cu(II) salts in the presence of the isomeric phenylenediacetic acids under hydrothermal conditions afforded three new coordination networks, {[Cu(L)(1,2-pda)]·H2O}n (1,2-H2pda = 1,2-phenylenediacetic acid), 1, {[Cu(L)(1,3-pda)]·2H2O}n (1,3- H2pda = 1,3-phenylenediacetic acid), 2, and {[Cu(L)(1,4-pda)]·2H2O}n (1,4-H2pda = 1,4-phenylenediacetic acid), 3, which have been structurally characterized by X-ray crystallography. Complex 1 forms a single 3,5-coordinated 3D net with the (42·65·83)(42·6)-3,5T1 topology, which can be further simplified as a 6-coordinated (412·63)-pcu topology. Complex 2 is a 5-fold interpenetrated 3D structure with the (65·8)-cds topology, which exhibits the maximum number of interpenetration presently known for cds and complex 3 is the first 1D self-catenated coordination network. The ligand isomerism of the phenylenediacetate ligands is important in determining the structural types of the Cu(II) coordination networks based on the flexible L ligands.

Two three-dimensional (3D) coordination networks, [Co3(1,4-BDC)3(L1)]∞ (L1 = N,N′-bis(3-pyridinyl)-1,4-benzenedicarboxamide; 1,4-H2BDC = 1,4-benzenedicarboxylic acid), 1, and [K2Co3(L2)4]∞ (H2L2 = 5-acetamidoisophthalic acid), 2, have been synthesized by hydrothermal reactions and characterized by single crystal X-ray crystallography. Complex 1 consists of linear trinuclear Co(II) centers, which are linked by the 1,4-BDC− and L1 ligands to form a rare (1 + 3) self-catenated 3D net with the new (36,410,511,6) topology, and complex 2 reveals a 3p–3d heterometallic coordination network based on linear trinuclear Co(II) and dinuclear K(I) centers bridged by the μ6-L2 ligands, forming a 4,4,8-connected trinodal net with the new (414·610·84)(42·64)(44·62) topology. The linear trinuclear Co(II) centers in 1 adopt the square pyramidal–octahedral–square pyramidal geometries, whereas those in 2 are tetrahedral–octahedral–tetrahedral. Both of the complexes exhibit paramagnetism that is consistent with the Curie–Weiss law between 60 and 300 K. The effective magnetic moments (〈μeff〉) of both complexes are larger than the estimated value of 6.71 μB/f.u., revealing the spin–orbit couplings that are invoked by the different distorted geometries of the linear trinuclear Co(II) centers. The dinuclear K(I) centers in 2 weaken the magnetic coupling, and reduce the antiferromagnetic ordering at 6 K.

A chiral-at-metal Ir(III) organometallic metallatecton was synthesised as a racemic mixture and as enantiopure complexes and combined with Cu(II) to afford a heterobimetallic (Ir,Cu) grid-type 2D coordination network.

A coordination network composed of a mannose-based organic ligand and a sodium ion, 'sugar sponge', was synthesized for the crystalline sponge analysis of hydrophilic compounds. Owing to multiple hydrogen-bonding interactions, hydrophilic guests are firmly trapped in the 1-dimensional channel. The sugar sponge was utilized to analyze the structures of flexible alcohol and absolute configurations of chiral epoxides.

Lone pair-π interaction-induced charge-transfer was successfully used for switching the conductance of a coordination network, through variation of the degree of charge transfer caused by external photostimulation. The underlying mechanism is attributed to the changes in efficient charge-carriers by photoinduced strong charge transfer, which was investigated by in situ UV-Vis absorption, ESR, and computational studies.

A Zn-based porphyrin containing metal–organic material (porphMOM-1) was transformed into a novel Cu-based porphyrin-encapsulating metal–organic material (porph@HKUST-1-β) via a one-pot post-synthetic modification (PSM) process involving both metal ion exchange and linker installation of trimesic acid. HKUST-1-β is the first example of yao topology and is to our knowledge the first supramolecular isomer of the archetypal coordination network HKUST-1.

A range of supramolecular complexes of O3S2-donor (L1-L3) and O2S3-donor (L4) macrocycles with different ring sizes (L1: 16-membered, L2: 17-membered, L3 and L4: 18-membered) were synthesized and structurally characterized. For the 11 complexes (1–11), the structural topologies and the types of coordination modes including mono- to multinuclear and endo- to exocyclic ones via M–S bonds have been discussed in terms of the possible exocoordination modes proposed. The reactions of L1, L3, and L4 with the silver(I) salts (BF4– and CF3COO–) afforded four complexes 1–4 with different topologies: two endocyclic mononuclear complexes [Ag(L1)NO3] (1) and [Ag(L1)]BF4 (2), and two exocyclic complexes [Ag(L3)(CF3COO)]n (3) and [Ag2(L4)2(CF3COO)2] (4) with a two-dimensional (2D) coordination network and cyclic dimer structures, respectively. In the reactions with copper(I) iodide, L1–L4 afforded the Cu4I4-cubane linked 2D coordination polymer {[(Cu4I4)(L1)2]·CH2Cl2}n (5), one-dimensional (1D) tubular coordination poly...

An unusual zinc(II) coordination polymer [Zn5(OH)2(bbtz)2(bdc)4]n (1) [bbtz1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, bdc1,2-benzenedicarboxylate] was synthesized and characterized. 1 contains an unusual 2D network based on pentanuclear zinc(II) cluster [Zn5(OH)2]. Two adjacent pentanuclear Zn(II) clusters are bridged by four bdc ligands and extend to form the one-dimensional chain. The bbtz ligands further link the one-dimensional chains, resulting in a two-dimensional coordination network. The luminescence and thermal stability were investigated.

Single-crystal X-ray analysis of a series of six silver(I) trifluoroacetate complexes containing designed ligands each composed of a functionalized cis- or trans-stilbene skeleton bearing two terminal ethynyl groups at variable ring positions provided detailed information on the influence of ligand disposition and orientation, coordination preferences, and coexistence of different types of silver(I)–carbon bonding (silver–ethynide, silver–ethenyl and silver–aromatic) in the construction of a coordination network, which are consolidated by argentophilic and weak intra/intermolecular interactions. The complex 3(Ag2L6)·14AgCF3CO2·[Ag2(CH3CN)3](CF3CO2)2·4H2O·6CH3CN [H2L6 = (E)-1,2-bis(4-ethynylphenyl)ethene] is the first reported example in which an ethynide terminal is bound by six silver(I) ions.

A metal-bearing coordination network synthesised from Re(2,2′-bipyridine-5,5′-dicarboxylate)(CO)3Cl bridging ligands and Cu(II) nodes, [{Cu(DMF)(H2O)[LRe(CO)3Cl]}·DMF]∞ReCu, undergoes an irreversible photoinduced charge transfer process. We demonstrate using time-resolved IR spectroscopy the nature of this photoinduced process and how, under suitable conditions, it is possible to initiate irreversible modification of the crystal through induction of the charge transfer process. As a result we are able to use the photoinduced process, which arises purely as a result of the structure of the coordination network, to write on crystals.

A net gain: A kinetically assembled, but thermally stable network is obtained using the labile metal species [Cu4 I4 (PPh3 )4 ]. The network uniquely adsorbs I2 by chemisorption through I3 (-) formation. The chemisorbed I2 readily desorbs above 380 K owing to the dynamic motion of the framework. A thermodynamically assembled network physisorbs I2 , which is an exact fit for the channel.

A new 3d-4f coordination polymer {[Sm2Ni(Pdc)2(SO4)2(H2O)6] · H2O} n (H2Pdc = pyridine-3,5-dicarboxylic acid) has been synthesized under hydrothermal conditions and structurally determined by X-ray diffraction method. The X-ray diffraction analysis reveals the compound crystallizes in the triclinic system, space group $$P\bar 1$$ , with a = 10.062(4), b = 10.249(4), c = 12.744(5) A, α = 93.548(4)°, β = 102.601(4)°, γ = 94.022(3)°, V = 1275.4(8) A3, F(000) = 972, M r = 1077.85, Z = 2, ρ c = 2.624 g cm−3, μ = 5.55 mm−1, final R = 0.0299, wR = 0.0805 for 4716 independent reflections with R int = 0.0204. According to the structure determination the complex is a three-dimensional (3D) network structure in which infinite lanthanide-carboxylate chains are linked by [Ni(SO4)2]2− metalloligands to form a mixed-metal coordination network.

A new metal–organic framework (MOF) based on metal clusters as secondary building units (SBU), has been synthesized and structurally characterized. The reported MOF presents an interesting 8-connected self-penetrating coordination network based on dinuclear cadmium cluster with a 4 24 ·5·6 3 topology. Moreover, the thermal stability and luminescence property of this compound have been investigated.

A novel body-centered cubic antiferromagnetic heterometal-coordination network Na4Mn8(μ4-OMe)6(μ4-MeCO2)12 ·2MeCO2 based on Mn8@Na8 cube-in-cube supramolecular building blocks has been synthesized, in which the unprecedented cubic (39.46)8 topological Mn8(μ4-OMe)6 cube with capped oxygen of five coordination is first revealed. Interestingly, the cube-in-cube Mn8@Na8 in combination with coordinated oxygen atoms makes up the unique nested Mn8O6@O24@Na8 triple-shell structure, in which the inner Mn8 cube is penetrated by the O6 octahedron but is enclosed by a larger O24 truncated cube that is further surrounded by a still larger Na8 cube.