Allosteric deprogramming of a trinuclear heterometallic helicate

Two multidentate ditopic ligands L1 and L2 which contain both N-donor and crown ether units have been synthesised. The potentially octadentate ligand L1 forms a trinuclear heterometallic double helicate with Cu(I) and Zn(II) ([Zn2Cu(L1)2](5+)), whereas L2 forms a tetranuclear heterometallic double helicate with the same metal ions ([Zn2Cu2(L2)2](6+)). Both species have been characterised by (1)H NMR, ESI-MS and single crystal X-ray crystallography. Reaction of [Zn2Cu2(L2)2](6+) with Ba(2+) results in the coordination of the crown ether units giving the simple barium coordinated species [Zn2Cu2(L2)2Ba2](10+). However, reaction of [Zn2Cu(L1)2](5+) with Ba(2+) deprograms the ligand and results in the formation of a mixture of species.     

This facile interconversion of dinuclear double helicates and side-by-side species: a reprogrammable ligand with potential sensor applications

The ligand L1 forms a dinuclear double helicate with Cu+ but upon addition of Ba2+ to the system a side-by-side species is formed both in solution and in the solid state; in the presence of Na+ both the helicate and the side-by-side species are formed in roughly equal amounts in solution.     

Localization and delocalization in a mixed-valence dicopper helicate

The coordination chemistry of the tetradentate pyridyl-thiazole (py-tz) N-donor ligand 6,6'-bis(4-phenylthiazol-2-yl)-2,2'-bipyridine (L1) has been investigated. Reaction of L1 with equimolar copper(II) ions results in the formation of the single-stranded mononuclear complex [Cu(L1)(ClO4)2] (1), whereas reaction with copper(I) ions results in the double-stranded dinuclear helicate [Cu2(L1)2][PF6]2 (2). Both complexes were characterized by X-ray crystallography, UV-vis spectroscopy, and electrospray ionization mass spectroscopy (as well as 1H NMR spectroscopy for diamagnetic 2). Complex 2 is redox-active and, upon one-electron oxidation, forms the stable tricationic mixed-valence helicate [Cu2(L1)2]3+ (3). This species can also be prepared in situ by combining [Cu(MeCN)4][BF4], [Cu(H2O)6][BF4]2, and L1 in a 1:1:2 ratio in nitromethane. X-ray crystallographic analysis of 3 provides structural evidence for the presence of an internuclear Cu-Cu bond, with an even distribution of spin density across the two Cu centers. Room-temperature UV-vis spectroscopy is consistent with this finding; however, frozen-glass EPR spectroscopic investigations suggest solvatochromic behavior at 110 K, with the [Cu2]3+ core varying from localized to delocalized depending on the solvent polarity.     

Proton-controllable fluorescent switch based on interconversion of polynuclear and dinuclear copper(II) complexes

The first reversible interconversion process between a one-strand polymeric copper(II) complex {[Cu2(L1)2(ClO4)2](ClO4)2}n (1) and a dicopper(II) helicate [Cu2(L1-2H)2] (2), proceeding via a deprotonation-protonation process, can transduce fluorescence and function as a fluorescent switch simply by introducing a one fiftieth equivalent of coumarine 343 anion, a fluorophore.     

Endogenous arene hydroxylation promoted by copper(I) cluster helicates

A novel neutral triple-stranded hexanuclear copper(I) cluster helicate [Cu(I)(6)L(3)]·2CH(3)CN derived from a thiosemicarbazone ligand could be synthesized and crystallographically characterized. The MALDI mass spectrum of this complex suggests that the tetranuclear copper(I) cluster helicate [Cu(I)(4)L(2)] is also present in solution. These copper(I) cluster helicates are capable, in the presence of O(2), of hydroxylating the arene linker of their supporting ligand strands. The resulting dinuclear complex [Cu(II)(2)L'(OH)] is formed by two copper(II) centers, a new ligand arising from the hydroxylation reaction, and one hydroxide group. The magnetic investigation of this compound shows a strong antiferromagnetic coupling between the two Cu(II) centers. The kinetic studies for the hydroxylation process show values of ΔH(≠)=-70 kJ mol(-1), similar to those mediated by the tyrosinase enzymes.     

Metal-dependent assembly of a helical-[Co3L3] cluster versus a meso-[Cu2L2] cluster with O,N,N',O'-Schiff base ligand: structures and magnetic properties

Self-assembly of a tetradentate ligand, N, N'-bi(salicylidene)-2,6-pyridinediamine (H 2L), with Cu(II) or Co(II), affords a dinuclear [Cu 2L 2] complex ( 1) or a trinuclear [Co 3L 3] complex ( 2), which were characterized by the single crystal X-ray diffraction study. The coordination geometry of the Cu (II) centers in 1 is between square planar and tetrahedral, with the ligand adopting a cis-cis conformation to give a centrally symmetric structure, which can be regarded as a mesocate. However, the coordination geometry of Co (II) centers in 2 is distortedly tetrahedral, and the ligand adopts a cis-trans conformation. The whole complex of 2 is of a pseudo- C 3 symmatrical, torus-like structure, which can be regarded as a circular helicate. Both the mesocate and the helicate exhibit expanded supramolecular structures due to elaborate intercomplex pi-stacking interactions. These two complexes were also characterized by element analysis, IR spectra, and TGA. To verify the stability of 2, ESI-MS was carried out on both the crystal and the powdered samples. Variable temperature magnetic susceptibility measurements reveal that both 1 and 2 display antiferromagnetic properties. DFT calculations were carried out on 1 to verify the antiferromagnetic coupling between intracluster metal centers.     

Asymmetric transformation of a double-stranded, dicopper(I) helicate containing achiral bis(bidentate) Schiff bases

Reactions of the bis(bidentate) Schiff-bases N,N'-bis(6-alkyl-2-pyridylmethylene)ethane-1,2-diamine (where alkyl = H, Me, iPr) (L) with tetrakis(acetonitrile)copper(I) hexafluorophosphate and silver(I) hexafluorophosphate afforded, respectively, the double-stranded, dinuclear metal helicates [T-4-(R,R)]-(+/-)-[M2L2](PF6)2 (M = Cu, Ag). The helicates were characterized by 1H and 13C NMR spectroscopy, conductivity, microanalysis, and single-crystal X-ray structure determinations on selected compounds. Intermolecular ligand exchange and intramolecular inversion rates for the complexes were investigated by 1H NMR spectroscopy. Reversible intermolecular ligand exchange between two differently substituted helicates followed first-order kinetics. The rate constants (k) and corresponding half-lives (t(1/2)) for ligand exchange for the dicopper(I) helicates were k = (1.6-1.8) x 10(-6) s(-1) (t(1/2) = 110-120 h) in acetone-d6, k = 4.9 x 10(-6) s(-1) (t(1/2) = 40 h) in dichloromethane-d2, and k > 2 x 10(-3) s(-1) (t(1/2) < 5 min) in acetonitrile-d3. Ligand exchange for the disilver(I) helicates occurred with k > 2 x 10(-3) s(-1) (t(1/2) < 5 min). Racemization of the dicopper(I) helicate by an intramolecular mechanism was investigated by determination of the coalescence temperature for the diastereotopic isopropyl-Me groups in the appropriate complex, and DeltaG() > 76 kJ mol(-1) was calculated for the process in acetone-d6, nitromethane-d3, and dichloromethane-d2 with DeltaG() = 75 kJ mol(-1) in acetonitrile-d3. Complete anion exchange of the hexafluorophosphate salt of a dicopper(I) helicate with the enantiomerically pure Delta-(-)-tris(catecholato)arsenate(V) ([As(cat)3]-) in the presence of Dabco gave the two diastereomers (R,R)-[Cu2L2][Delta-(-)-[As(cat)3]]2 and (S,S)-[Cu2L2][Delta-(-)-[As(cat)3]]2 in up to 54% diastereomeric excess, as determined by (1)H NMR spectroscopy. The diastereomerically and enantiomerically pure salt (R,R)-[Cu(2)L2][Delta-(-)-[As(cat)3]]2 crystallized from the solution in a typical second-order asymmetric transformation. The asymmetric transformation of the dicopper(I) helicate is the first synthesis of a diastereomerically and enantiomerically pure dicopper(I) helicate containing achiral ligands.     

Cu(I) and Cu(II) helical complexes formed with oligobipyridine ligand

A new asymmetric oligobipyridine ligand, 1- (5’-methyl-2, 2’-bipyridin-5-y1)-2- (6’-methyl-2, 2’-bipyridin-6-yl)ethane (L), in which the bipyridine units are bridged by CH₂CH₂ at 5,6’-position has been synthesized. The ligand L reacts with Cu(I) and Cu(I1) ions giving double-stranded helical complexes [Cu ₂ ¹ L₂](C10₄)₂.Et₂0 (1) and [Cu ₂ ^II L₂,(OH)(H₂0) ] [ClO₄]₃(2), respectively. Complexes 1 and 2 were characterized by X-ray diffraction analyses, ES-MS, ESR and cyclic voltammetry, etc. Differing from the oligobipyridine ligands bridged by CH₂CH₂ at 6,6’-or 5,5’-position, the ligand L not only forms a double-stranded helicate with Cu(1) ion, but also gives a double-stranded helicate with Cu(I1) ion. The results show that the linkage mode of the spacer group to the bipyridine units exerts a great impact on the formation of helix. Project supported by the National Natural Science Foundation of China (Grant NO. 29601003).     

DNA three-way junction with a dinuclear iron(II) supramolecular helicate at the center: a NMR structural study

A tetracationic supramolecular helicate, [Fe2L3]4+ (L = C25H20N4), with a triple-helical architecture is found to induce the formation of a three-way junction (3WJ) of deoxyribonucleotides with the helicate located in the center of the junction. NMR spectroscopic studies of the interaction between the M enantiomer of the helicate and two different oligonucleotides, [5'-d(TATGGTACCATA)]2 and [5'-d(CGTACG)]2, show that, in each case, the 2-fold symmetry of the helicate is lifted, while the 3-fold symmetry around the helicate axis is retained. The 1:3 helicate/DNA stoichiometry estimated from 1D NMR spectra supports a molecular model of a three-way junction composed of three strands. Three separate double-helical arms of the three-way junction are chemically identical giving rise to one set of proton resonances. The NOE contacts between the helicate and DNA unambiguously show that the helicate is fitted into the center of the three-way junction experiencing a hydrophobic 3-fold symmetric environment. Close stacking interactions between the ligand phenyl groups and the nucleotide bases are demonstrated through unusually large downfield shifts (1-2 ppm) of the phenyl protons. The unprecedented 3WJ arrangement observed in solution has also been found to exist in the crystal structure of the helicate adduct of [d(CGTACG)2] (Angew. Chem., Int. Ed. 2006, 45, 1227).     

Ligand Reprogramming in Dinuclear Helicate Complexes: A Consequence of Allosteric or Electrostatic Effects?

The ditopic ligand 6,6'-bis(4-methylthiazol-2-yl)-3,3'-([18]crown-6)-2,2'-bipyridine (L(1)) contains both a potentially tetradentate pyridyl-thiazole (py-tz) N-donor chain and an additional "external" crown ether binding site which spans the central 2,2'-bipyridine unit. In polar solvents (MeCN, MeNO(2)) this ligand forms complexes with Zn(II), Cd(II), Hg(II) and Cu(I) ions via coordination of the N donors to the metal ion. Reaction with both Hg(II) and Cu(I) ions results in the self-assembly of dinuclear double-stranded helicate complexes. The ligands are partitioned by rotation about the central py--py bond, such that each can coordinate to both metals as a bis-bidentate donor ligand. With Zn(II) ions a single-stranded mononuclear species is formed in which one ligand coordinates the metal ion in a planar tetradentate fashion. Reaction with Cd(II) ions gives rise to an equilibrium between both the dinuclear double-stranded helicate and the mononuclear species. These complexes can further coordinate s-block metal cations via the remote crown ether O-donor domains; a consequence of which are some remarkable changes in the binding modes of the N-donor domains. Reaction of the Hg(II)- or Cd(II)-containing helicate with either Ba(2+) or Sr(2+) ions effectively reprogrammes the ligand to form only the single-stranded heterobinuclear complexes [MM'(L(1))](4+) (M=Hg(II), Cd(II); M'=Ba(2+), Sr(2+)), where the transition and s-block cations reside in the N- and O-donor sites, respectively. In contrast, the same ions have only a minor structural impact on the Zn(II) species, which already exists as a single-stranded mononuclear complex. Similar reactions with the Cd(II) system result in a shift in equilibrium towards the single-stranded species, the extent of which depends on the size and charge of the s-block cation in question. Reaction of the dicopper(I) double-stranded helicate with Ba(2+) shows that the dinuclear structure still remains intact but the pitch length is significantly increased.     

A triple helix of double helicates: three hierarchical levels of self-assembly in a single structure

The bis-bidentate bridging ligand L reacts with Ag(I) ions to form a conventional dinuclear [Ag(2)L(2)](2+) double helicate; individual double helicate units assemble via Ag···Ag interactions into infinite chains, three of which wrap around a central spine of anions to give a triple helical braid, which is therefore an infinite triple helix composed of molecular double helicate subunits.     

Molecular squares, cubes and chains from self-assembly of bis-bidentate bridging ligands with transition metal dications

The two new ligands L(fur) and L(th) consist of two chelating pyrazolyl-pyridine termini connected to furan-2,5-diyl or thiophene-2,5-diyl spacers via methylene groups. Reaction of these with a range of transition metal dications that prefer octahedral coordination affords a series of unusual structures which are all based on a 2M : 3L ratio. [M(8)(L(fur))(12)]X(16) (M = Co, Cu, X = BF(4); and M = Zn, X = ClO(4)) are octanuclear cubes with approximate D(4) symmetry in which two cyclic tetranuclear helicate M(4)L(4) units are connected by four additional 'pillar' ligands. In contrast [Ni(4)(L(fur))(6)](BF(4))(8) is a centrosymmetric molecular square consisting of two dinuclear Ni(2)L(2) units of opposite chirality that are connected by a pair of additional L(fur) ligands such that the four edges of the Ni(4) square are spanned by alternately two and one bridging ligands. [M(4)(L(th))(6)](BF(4))(8) (M = Co, Ni, Cu) are likewise molecular squares with similar structures to [Ni(4)(L(fur))(6)](BF(4))(8) with the significant difference that the two crosslinked double helicate M(2)L(2) units are now homochiral. The Cd(II) complexes both behave quite differently to the first-row metal complexes, with [Cd(L(fur))(BF(4))](BF(4)) being a simple mononuclear complex with a single ligand in which the furan oxygen atom is weakly interacting with the Cd(II) centre. In contrast, in {[Cd(2)(L(th))(3)](BF(4))(4)}(∞), where this quasi-pentadentate coordination mode of the ligand is not possible because thiophene is too poor an electron donor, the ligand reverts to bis-bidentate bridging coordination to afford a one-dimensional chain consisting of an infinite sequence of crosslinked, homochiral, Cd(2)(L(th))(2) double helicate units.     

Monitoring the redox-driven assembly/disassembly of a dicopper(I) helicate with an auxiliary fluorescent probe

The assembly/disassembly of a dicopper(I) helicate with a bis-bidentate imine-quinoline ligand is driven by the Cu(II)/Cu(I) redox change and is signaled by a fluorescent probe bearing a -COO(-) group (coumarine 343). The probe coordinates the Cu(II) center of the monomeric complex, which quenches its emission (fluorescence off), and is released upon reduction and formation of the Cu(I) helicate (fluorescence on).     

From homoleptic to heteroleptic double stranded Copper(I) helicates: the role of self-recognition in self-assembly processes

The ligands 2,9-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-1,10-phenanthroline (6), 6' ',6' "-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl)]-2' ',2' "-bipyridine (2), 5,5'-bis[(6-methyl-2,2'-bipyridin-6'yl)methyleneoxymethylenyl]-2, 2'-bithiophene (7), and 6,6'-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-2,2'-biphenyl (8) and their respective homo- and heteroleptic double-stranded copper(I) complexes were prepared and characterized in order to estimate the importance of self-recognition in the self-assembly processes of double-stranded copper complexes. The homoleptic double-stranded copper complexes of 2, 6, 7, and 8 were characterized by NMR, FAB-MS, and electrochemistry. It was found that 6 and 2 each form a single double-stranded helicate having the structure of [(L)(2)Cu(3)](3+) (L = 2 or 6), 7 forms two double-stranded [(7)(2)Cu(3)](3+) complexes, and 8 results in a mixture of at least two [(8)(2)Cu(2)](2+) complexes. The potential shift, DeltaE degrees (,) of the Cu(+)/Cu(2+) redox process of these complexes reflects the binding affinity of the different binding sites to the copper cation. The electrochemical data show that the central units have a higher affinity to Cu(+) as compared to the off-center binding sites. NMR was used to determine the actual complex composition obtained from different mixtures of 2, 6, or 7 with Cu(+). Interestingly, we have found that, although 6, 2, and 7 each form homoleptic double-stranded complexes, no heteroleptic double-stranded copper complexes were formed from the mixtures of 7 with either 6 or 2. However, when mixtures of 6 and 2 are used, helicate distributions seem to follow simple statistics. These results are discussed in terms of the relative importance of self-recognition in the self-assembly of double-stranded helicates.     

Anion control of ligand self-recognition in a triple helical array

Self-assembly of the ligand L(1) with Co(2+) into a dinuclear triple helicate [Co(2)(L(1))(3)](4+) produces an anion binding pocket which encapsulates perchlorate anions. Furthermore we demonstrate how this ability to bind anions can control ligand self-recognition properties.     

Heterometallic compounds assembled from ferrocene-containing bisthiosemicarbazone clips

Heteropolynuclear organometallic compounds have been constructed by using the ferrocene-based ligand H(2)L, [NH(2)SCNHN=C(CH(3))(C(5)H(4))](2)Fe. Reaction of the ligand H(2)L with the cobalt(II) salt gave a tetranuclear helicate Co(2)Fe(2) (1) with two ferrocene-based clips wrapped around the two cobalt atoms. The chiral helicates recognized the neighbors with same chirality through intermolecular hydrogen bonding between the thiosemicarbazone moieties to form a one-dimensional chiral channel. Reaction of the ligand H(2)L with the cadmium(II) salt afforded a tetranuclear dimeric compound Cd(2)Fe(2) (2), with two symmetric related parts bridged through two sulfur atoms. Reaction of the ligand H(2)L with the copper(I) salt, in the presence of triethylamine, resulted in a hexanuclear compound Cu(4)Fe(2) (3) with a crownlike Cu(4)S(4) octagon similar to that of S(8) sited inside and two ferrocene-containing ligands positioned outside. Electrochemical measurements were displayed to investigate the redox communications between the ferrocene moieties through metal centers.     

Structure and properties of a new double-stranded tetranuclear [Cu(II)2]2 helicate

A novel double-stranded tetranuclear helicate composed of a pair of [Cu(II)(2)] dimers has been prepared and characterized by exploiting the flexibility, chelating ability and bridging potential of a hexadentate bis-oximate ligand.     

Hexanuclear copper(II) cage with {Cu3O···H···OCu3} core supported by a dicompartmental oxime ligand with m-xylyl spacer: synthesis, molecular structure and magnetic studies

A new dicompartmental dioxime ligand (H(2)L) with m-xylyl spacer between the donor sites has been synthesised by Schiff-base condensation of α,α'-diamino-m-xylene and diacetyl monooxime. The ligand reacts with copper(ii) salts giving rise to hexanuclear tricationic copper(II) cage complexes [Cu(II)(6)(μ(3)-O···H···O-μ(3))L(3)(H(2)O)(6)]X(3) (X = BF(4), 1a; X = ClO(4), 1b). The complexes have been characterised by different analytical and spectroscopic techniques and confirmed the hexanuclear structure even in solution. Single crystal X-ray diffraction studies of both the complexes revealed a very similar core structure with three dicompartmental ligands supporting two triangular Cu(3)O cores that share a proton, located on their common threefold axis and involved in a strong hydrogen bond interaction (O···O distance of 2.517(2) ?). Two Cu(3)O units do not superimpose but are staggered and disposed with the formation of a helicate structure. However both the enantiomers are present in the centrosymmetric space group. The facing Cu(3)-planes in 1a are separated at a distance of 3.476 ?. The temperature dependence of the magnetic behaviour of the hexanuclear complex 1a clearly indicates an overall antiferromagnetic exchange interaction between the spin carriers in the cage having two Cu(3)O subunits and leaves a single unpaired electron in each triangular unit. The unpaired electrons in the two Cu(3)O units interact antiferromagnetically through hydrogen bonding giving rise to an overall singlet-spin ground state.     

Efficient resolution of a dinuclear triple helicate by asymmetric extraction/precipitation with TRISPHAT anions as resolving agents

Tetradentate 1,2-bis[4-(4'-methyl-2,2'-bipyridyl)]ethane ligand (3) and Fe(NH4)2(SO4)2.6H2O combine in a 3:2 ratio to form the racemic helicate [Fe2L3]4+ (4), as reported by Elliott et al. We now show that the enantiomeric purity of 4 can be efficiently measured by 1H NMR by the use of the TRISPHAT (1) salt as a chiral shift reagent. Large differences in chemical shifts (deltadeltadelta of up to 0.3 ppm, 20% [D6]DMSO in CD3CN) are observed between the enantiomers of 4 upon addition of [nBu4N][delta-1]. The resolution of 4 by asymmetric extraction was attempted: addition of an organic solution of [cinchonidinium][delta-1] salt (2 equiv) to an aqueous solution of helicate 4-(SO4)2 led, after vigorous stirring, to the extraction of the homochiral diastereomer [P-4][delta-1]4 into the organic layer along with the precipitation of the heterochiral diastereomer [M-4][delta-1]4 at the interface (diastereomeric ratio>49:1 for both processes). An enantioenriched fraction of [P-4][SO4]2 remained in the aqueous layer. To obtain only two fractions of resolved helicate and develop this procedure into an efficient resolution protocol, four equivalents of [cinchonidinium][delta-1] salt were used as the resolving agent. Chemically and diastereomerically pure [P-4][delta-1]4 and [M-4][delta-1]4 helicate salts were then obtained in excellent yields.