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ZnII Ion (znii + ion)
Selected AbstractsReceptor versus Counterion: Capability of N,N, -Bis(2-aminobenzyl)-diazacrowns for Giving Endo- and/or Exocyclic Coordination of ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007Lea Vaiana Abstract The structure of ZnII complexes with receptors L1 and L2[L1 = N,N, -bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and L2 = N,N, -bis(2-aminobenzyl)-4,13-diaza-18-crown-6] was studied both in the solid state and in acetonitrile solution. Both receptors form mononuclear ZnII complexes in this solvent, while no evidence for the formation of dinuclear complexes was obtained. This is in contrast with previous investigations that demonstrated the formation of dinuclear complexes of L2 with first-row transition metals such as NiII, CoII and CuII. Compounds of formula [Zn(L1)](ClO4)2 (1), [Zn(L1)](NO3)2·2CH3CN (2), [Zn(L2)](ClO4)2 (3) and [Zn(L2)(NO3)2] (4) were isolated and structurally characterised by X-ray diffraction analyses. L1 forms seven-coordinate ZnII complexes in the presence of both nitrate and perchlorate anions, as a consequence of the good fit between the macrocyclic cavity and the ionic radius of the metal ion. The ZnII ion is deeply buried into the receptor cavity and the anions are forced to remain out of the metal coordination sphere. The cation [Zn(L1)]2+ present in 1 and 2 is one of the very few examples of seven-coordinate Zn complexes. Receptor L2 provides a very rare example of a macrocyclic receptor allowing endocyclic and exocyclic coordination on the same guest cation, depending on the nature of the anion present. Thus, in 3 the ZnII ion is endocyclically coordinated, placed inside the crown hole coordinated to four donor atoms of the ligand in a distorted tetrahedral environment, whereas in 4, the presence of a strongly coordinating anion such as nitrate results in an exocyclic coordination of ZnII, which is directly bound only to the two primarily amine groups of L2 and two nitrate ligands. Spectrophotometric titrations of [Zn(L2)]2+ with tetrabutylammonium nitrate in acetonitrile solution demonstrate the stepwise formation of 1:1 and 1:2 adducts with this anion in acetonitrile solution. The [Zn(L1)]2+, [Zn(L2)]2+ and [Zn(L2)(NO3)2] systems were characterised by means of DFT calculations (B3LYP model). The calculated geometries show an excellent agreement with the experimental structures obtained from X-ray diffraction analyses. Calculated binding energies of the macrocyclic ligands to ZnII are also consistent with the experimental data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] A Metal,Macrocycle Complex as a Fluorescent Sensor for Biological Phosphate Ions in Aqueous SolutionEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 10 2010Xiao-huan Huang Abstract We synthesized tetraazamacrocycles 1 and 2 bearing two anthryl groups as sidearms, both of which exhibited high selectivity for the ZnII ion in switching-on-type responses in aqueous solution. For ligand 1, ZnII is coordinated by four nitrogen atoms of the macrocycle and two amino groups on the pendent arms, which results in proximity between the twofluorophores. So, 1 -ZnII shows obvious excimer emission in aqueous solution. When PPi or ATP was added (pH 7.4), the excimer emission of 1 -ZnII was quenched, whereas monomer emission was revived. To the best of our knowledge, no other known sensor has this characteristic under physiological pH conditions. At the same time, the obvious different fluorescence response of 1 -ZnII for PPi and ATP in water shows that receptor 1 -ZnII can be used as a selective fluorescent chemosensor for PPi and ATP anions. [source] Second-Generation Inhibitors for the Metalloprotease Neprilysin Based on Bicyclic Heteroaromatic Scaffolds: Synthesis, Biological Activity, and X-Ray Crystal-Structure AnalysisHELVETICA CHIMICA ACTA, Issue 4 2005Stefan Sahli A new class of nonpeptidic inhibitors of the ZnII -dependent metalloprotease neprilysin with IC50 values in the nanomolar activity range (0.034,0.30,,M) were developed based on structure-based de novo design (Figs.,1 and 2). The inhibitors feature benzimidazole and imidazo[4,5- c]pyridine moieties as central scaffolds to undergo H-bonding to Asn542 and Arg717 and to engage in favorable , - , stacking interactions with the imidazole ring of His711. The platform is decorated with a thiol vector to coordinate to the ZnII ion and an aryl residue to occupy the hydrophobic S1, pocket, but lack a substituent for binding in the S2, pocket, which remains closed by the side chains of Phe106 and Arg110 when not occupied. The enantioselective syntheses of the active compounds (+)- 1, (+)- 2, (+)- 25, and (+)- 26 were accomplished using Evans auxiliaries (Schemes,2, 4, and 5). The inhibitors (+)- 2 and (+)- 26 with an imidazo[4,5- c]pyridine core are ca. 8 times more active than those with a benzimidazole core ((+)- 1 and (+)- 25) (Table,1). The predicted binding mode was established by X-ray analysis of the complex of neprilysin with (+)- 2 at 2.25-Å resolution (Fig.,4 and Table,2). The ligand coordinates with its sulfanyl residue to the ZnII ion, and the benzyl residue occupies the S1, pocket. The 1H -imidazole moiety of the central scaffold forms the required H-bonds to the side chains of Asn542 and Arg717. The heterobicyclic platform additionally undergoes ,-, stacking with the side chain of His711 as well as edge-to-face-type interactions with the side chain of Trp693. According to the X-ray analysis, the substantial advantage in biological activity of the imidazo-pyridine inhibitors over the benzimidazole ligands arises from favorable interactions of the pyridine N-atom in the former with the side chain of Arg102. Unexpectedly, replacement of the phenyl group pointing into the deep S1, pocket by a biphenyl group does not enhance the binding affinity for this class of inhibitors. [source] A novel trinuclear zinc(II) cluster with a tetrahedral ZnO4 coreACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2009Orde Q. Munro The reaction of 0.67 molar equivalents of the O,N,O,-tridentate zwitterionic Schiff base (2Z,4E)-4-[(2-hydroxyphenyl)iminio]pent-2-en-2-olate (H2L) with one equivalent of zinc(II) acetate in methanol affords a novel trinuclear ZnII cluster, di-,-acetato-1:2,2O:O,;2:3,2O:O,-dimethanol-1,O,3,O -bis{,-2-[(2E,3Z)-4-oxidopent-3-en-2-ylideneamino]phenolato}-1:2,4O2,N,O4:O4;2:3,4O4:O2,N,O4 -trizinc(II), [Zn3(C11H11NO2)2(C2H3O2)2(CH4O)2], (I), in which two bridging acetate ligands link the terminal square-based pyramidal ZnII ions to the approximately tetrahedral ZnII ion at the core of the cluster. The ZnO4 coordination group of the central ZnII ion is established by two bridging phenolate and two bridging acetate O atoms. The remaining four coordination sites of each terminal ZnII ion are occupied by methanol and deprotonated H2L. Furthermore, the Zn-bound methanol hydroxyl groups are involved in complementary hydrogen bonding with the Zn-bound enolate O atom of a neighbouring molecule, about an inversion centre in each case. The structure of (I) is therefore best described as an extended one-dimensional hydrogen-bonded chain of trinuclear ZnII clusters. [source] A novel threefold-interpenetrating primitive cubic network based on a dinuclear Zn2 nodeACTA CRYSTALLOGRAPHICA SECTION C, Issue 2 2009Yun-Peng Diao In the mixed-ligand metal,organic polymeric compound poly[[,2 -1,4-bis(imidazol-1-yl)benzene](,2 -terephthalato)dizinc(II)], [Zn2(C8H4O4)2(C12H10N4)]n or [Zn2(bdc)2(bib)]n [H2bdc is terephthalic acid and bib is 1,4-bis(imidazol-1-yl)benzene], the asymmetric unit contains one ZnII ion, with two half bdc anions and one half bib molecule lying around inversion centers. The ZnII ion is in a slightly distorted tetrahedral environment, coordinated by three carboxylate O atoms from three different bdc anions and by one bib N atom. The crystal structure is constructed from the secondary building unit (SBU) [Zn2(CO2)2N2O2], in which the two metal centers are held together by two bdc linkers with bis(syn,syn -bridging bidentate) bonding modes. The SBU is connected by bdc bridges to form a two-dimensional grid-like (4,4)-layer, which is further pillared by the bib ligand. Topologically, the dinuclear SBU can be considered to be a six-connected node, and the extended structure exhibits an elongated primitive approximately cubic framework. The three-dimensional framework possesses a large cavity with dimensions of approximately 10 × 13 × 17,Å in cross-section. The potential porosity is filled with mutual interpenetration of two identical equivalent frameworks, generating a novel threefold interpenetrating network with an ,-polonium topology [Abrahams, Hoskins, Robson & Slizys (2002). CrystEngComm, 4, 478,482]. [source] Transition metal complexes with thiosemicarbazide-based ligands.ACTA CRYSTALLOGRAPHICA SECTION C, Issue 6 2002XLIII. In the title compound, [ZnCl(C2H7N3S)2]Cl, the ZnII ion is five-coordinated in a distorted trigonal,bipyramidal arrangement, with the hydrazine N atoms located in the apical positions. The structure is stabilized by N,H,Cl hydrogen bonds, which involve both the Cl atoms and all the hydrogen donors, except for one of the two thioamide N atoms. A comparison of the geometry of thiosemicarbazide and S -methylisothiosemicarbazide complexes with ZnII, CuII and NiII shows the pronounced influence of the hydrogen-bond network on the coordination geometry of ZnII compounds. [source] Novel Molecular Building Blocks Based on the Boradiazaindacene Chromophore: Applications in Fluorescent Metallosupramolecular Coordination PolymersCHEMISTRY - A EUROPEAN JOURNAL, Issue 15 2009Ö. Altan Bozdemir Dr. Abstract Bright polymers: Fluorescent coordination polymers made up of versatile functionalized bodipy (boron-dipyrrin) chromophore building blocks, such as that depicted, are described. Polymerization is signaled by changes in fluorescence emission intensity and shifts in peak emission wavelengths. We designed and synthesized novel boradiazaindacene (Bodipy) derivatives that are appropriately functionalized for metal-ion-mediated supramolecular polymerization. Thus, ligands for 2-terpyridyl-, 2,6-terpyridyl-, and bipyridyl-functionalized Bodipy dyes were synthesized through Sonogashira couplings. These fluorescent building blocks are responsive to metal ions in a stoichiometry-dependent manner. Octahedral coordinating metal ions such as ZnII result in polymerization at a stoichiometry corresponding to two terpyridyl ligands to one ZnII ion. However, at increased metal ion concentrations, the dynamic equilibria are re-established in such a way that the monomeric metal complex dominates. The position of equilibria can easily be monitored by 1H,NMR and fluorescence spectroscopies. As expected, although open-shell FeII ions form similar complex structures, these cations quench the fluorescence emission of all four functionalized Bodipy ligands. Bu çal,,mada, metal iyonlar, arac,l,,,yla supramoleküler polimerizasyon için uygun ,ekilde fonksiyonland,r,lm,, yeni boradiazaindasen (Bodipy) türevleri tasarlanm,, ve sentezlenmi,tir. Bu amaçla, ligand olarak Sonogashira reaksiyonu ile 2- ve 2,6-terpiridil ve bipiridil gruplar,n, içeren Bodipy boyarmaddeleri sentezlenmi,tir. Bu floresan yap, bloklar, stokiyometriye ba,l, bir biçimde metal iyonlar,na duyarl,l,k gösterirler. ZnIIgibi oktahedral koordinasyon e,ilimi olan metal iyonlar,, iki terpiridil ligand,na bir ZnIIiyonu tekabül edecek bir stokiyometride polimerizasyona yol açmaktad,rlar. Bununla beraber, yüksek metal iyonu deri,imlerinde monomerik metal kompleksinin bask,n olaca,, bir biçimde, dinamik dengeler yeniden kurulmaktad,r. Bu dengelerin pozisyonu1H,NMR ve fluoresans spektroskopileriyle kolayl,kla izlenebilmektedir. Beklenildi,i gibi, benzer kompleks yap,lar olu,turmas,na ra,men FeIIiyonu, sentezlenen tüm fonksiyonalize Bodipy ligandlar,n,n emisyonlar,n, sönümlendirmektedir. [source] Luminescent Excited-State Intramolecular Proton-Transfer (ESIPT) Dyes Based on 4-Alkyne-Functionalized [2,2,-Bipyridine]-3,3,-diol DyesCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2008Gilles Ulrich Dr. Abstract Functionalized 6,6,-dimethyl-3,3,-dihydroxy-2,2,-bipyridine dyes (BP(OH)2) exhibit relatively intense fluorescence from the relaxed excited state formed by excited-state intramolecular proton transfer (ESIPT). Bromo functionalization of (BP(OH)2) species followed by palladium(0)-catalyzed reactions allows the connection (via alkyne tethers) of functional groups, such as the singlet-emitter diazaboraindacene (bodipy) group or a chelating module (terpyridine; terpy). The X-ray structure of the terpy-based compound confirms the planarity of the 3,3,-dihydroxy-bipyridine unit. The new dyes exhibit relatively intense emission on the nanosecond timescale when in fluid solution, in the solid state at 298,K, and in rigid glasses at 77,K. In some cases, the excitation wavelength luminescence was observed and attributed to 1),inefficiency of the ESIPT process in particular compounds when not enough vibrational energy is introduced in the Franck,Condon state, which is populated by direct light excitation or 2),the presence of an additional excited state that deactivates to the ground state without undergoing the ESIPT process. For some selected species, the effect of the addition of zinc salts on the absorption and luminescence spectra was investigated. In particular, significant fluorescence changes were observed as a consequence of probable consecutive formation of a 1:1 and 1:2 molecular ratio of ligand/zinc adducts owing to coordination of ZnII ions by the bipyridyldiol moieties, except when an additional terpyridine subunit is present. In fact, this latter species preferentially coordinates to the ZnII ion in a 1:1 molecular ratio and further inhibits ZnII interaction. In the hybrid Bodipy/BP(OH)2 species, complete energy transfer from the BP(OH)2 to the bodipy fluorophore occurs, leading to exclusive emission from the lowest-lying bodipy subunit. Des composés colorés à base de 6,6,-dimethyl-3,3,-dihydroxy-2,2,-bipyridine (BP(OH)2) ont été synthétisés et présentent une fluorescence relativement intense issue de la relaxation d,un état excité provenant d,un transfert de proton dans l,état excité (ESIPT). La bromation de dérivés (BP(OH)2) suivie d,un couplage croisé catalysé par du Pd0sous-ligandé permet de connecter (par l,intermédiaire de pont alcyne) des groupes fonctionnels comme un groupe émetteur singulet de type boradiazaindacène (Bodipy) ou un module chélatant universel (une terpyridine). Une structure par diffraction aux rayons X a été obtenu avec le dérivé terpyridine, celle ci confirme la planéité de l,unité 3,3,-dihydroxy-bipyridine. Les nouveaux fluorophores possèdent une émission relativement intense avec une durée de vie de l,ordre de la nanoseconde, en solution et à l,état solide à 298,K ainsi que dans un verre à 77,K. Dans certain cas, la luminescence dépend de la longueur d,onde d,excitation, ce phénomène est attribué à (i) l,inefficacité du processus ESIPT, quand trop peu d,énergie vibrationnelle est introduite dans l,état Franck-Condon peuplé directement par la lumière d,excitation (ii) la présence d,un état excité supplémentaire qui désactive l,état fondamental sans passer par un processus ESIPT. Pour certains composés, l,effet de l,addition de sels de Zinc sur les spectres d,absorption et d,émission a été étudié : en particulier, des changements significatifs de fluorescence ont été observés, probablement due à la formation consécutive de complexes ligand/zinc de st,chiométrie 1:1 et 1:2, provenant de la coordination des cations ZnIIpar l,unité bipyridyl-diol, sauf quand une fonction terpyridine est présente. En fait, dans cette dernière espèce le zinc est préférentiellement coordiné par la terpyridine dans un ratio 1:1, et toute coordination supplémentaire de Zinc semble inhibée. Dans le composé hybride Bodipy/BP(OH)2,un transfert d,énergie quantitatif est observé du BP(OH)2vers le fluorophore Bodipy, entraînant une émission exclusive de la sous-unité Bodipy. Composti basati sulla subunità 6,6,-dimetil-3,3,-dididrossi-2,2,-bipiridina (BP(OH)2), variamente funzionalizzati, presentano fluorescenza relativamente intensa da stati eccitati formati attraverso trasferimento protonico nello stato eccitato (ESIPT). Bromo-funzionalizzazione dei composti di tipo BP(OH)2, seguita da reazioni catalizzate da Pd(0), permettono di connettere (con legame alchinico) gruppi funzionali quali il diazaboroindacene (Bodipy) o un modulo chelante (terpiridina) al frammento BP(OH)2. La struttura ai raggi X del composto contenente la terpiridina conferma la planarità dell,unità 3,3,-diidrossi-bipiridina. Le nuove specie presentano intensa emissione nella scala dei nanosecondi, in soluzione fluida ed allo stato solido a 298,K ed in matrice rigida a 77,K. In alcuni casi, la luminescenza dipende dalla lunghezza d,onda di eccitazione: questo fenomeno è attribuito a (i) inefficienza del processo ESIPT, quando non sufficiente energia vibrazionale è introdotta nello stato Franck-Condon a seguito di eccitazione luminosa o (ii) alla presenza di uno stato eccitato addizionale che si disattiva allo stato fondamentale senza passare dallo stato eccitato prodotto attraverso il meccanismo ESIPT. Per composti selezionati è stato anche studiato l,effetto della presenza di sali di zinco sulle proprietà di assorbimento elettronico e di luminescenza: significativi cambiamenti della fluorescenza sono stati osservati, come conseguenza della consecutiva formazione di addotti 1:1 e 1:2 (rapporto molare BP(OH)2/zinco), dovuta alla coordinazione di cationi di ZnIIda parte del bipiridil-diolo, che si verifica in tutti i casi studiati tranne in presenza di una subunità terpiridinica. In quest,ultimo caso, infatti, si forma soltanto l,addotto 1:1, e ulteriore coordinazione di cationi di ZnIIappare inibita. Nella specie ibrida Bodipy/BP(OH)2si verifica un completo trasferimento di energia elettronica dal BP(OH)2 al Bodipy, che porta ad emissione esclusivamente dalla subunità Bodipy, a piû bassa energia. [source] Allosteric Tuning of the Intra-Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side ChainsCHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2007Ulrich Darbost Dr. Abstract Molecular recognition by calix[6]arene-based receptors bearing three primary alkylamino side chain arms (1) is described. Complexation of ZnII ion provides the dinuclear ,-hydroxo complex , XRD characterization of which, together with solution studies, provided evidence of its hosting of neutral polar organic guests G. Treatment of this complex with a carboxylic acid or a sulfonamide (XH) results in the formation of mononuclear species , one of which (X = Cl) has been characterized by XRD. A dicationic complex is obtained upon treatment of with a mixture of an alkylamine and a strong acid. Each of these ZnII complexes features a tetrahedral metal ion bound to the three amino arms of ligand 1 and to an exogenous ligand (either HO,, X,, or RNH2) sitting outside of the cavity. As a result, the metal ion structures the calixarene core, constraining it in a cone conformation suitable for guest hosting. The receptor properties of these compounds have been explored in detail and are compared with those of the trisammonium receptor , based on the same calixarene core, as well as those of the trisimidazole-based dicationic Zn funnel complexes. This study reveals very different host properties, in spite of the common hydrophobic, ,-basic, and hydrogen-bonding acceptor properties of the calixarene cores. A harder external ligand produces a less polarized receptor that is consequently particularly sensitive to the hydrogen-bonding ability of its guest. The less electron-rich the apical ligand, and a fortiori the trisammonium host, the more sensitive the receptor to the dipole moment of the guest. All this stands in contrast with the funnel Zn complexes, in which the coordination link plays a dominant role. It is also shown that the asymmetry of an exo -coordinated enantiopure amino ligand is sensed by the guest. This supramolecular system nicely illustrates how the receptor properties of a hydrophobic cavity can be allosterically tuned by the environment. [source] Hybrid 2D and 3D Frameworks Based on ,-Keggin Polyoxometallates: Experiment and SimulationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2005Anne Dolbecq Abstract The ,-Keggin polyoxomolybdate {,-PMoV8MoVI4O40,x(OH)xM4} is a versatile building unit, with M being either a ZnII or a LaIII capping ion located at the vertices of a slightly distorted tetrahedron. The charge of the Keggin unit depends on the number of protonated oxo bridging ligands, which has been shown to vary from 0 to 5. The Keggin entity can thus be either an anion (M = Zn, x = 0) or a cation (M = La, x = 3,5). The Zn derivative has been generated in situ by hydrothermal synthesis and forms a 2D material built from the connection of the cations by 4,4'-bipyridine ligands linked to the capping ZnII ions. The reaction of the chloride salt of the La derivative with di-, tri- and tetrasubstituted benzenecarboxylate ligands has allowed us to isolate 2D and 3D materials. The 3D materials seem to be the first examples of hybrid open frameworks based on Keggin building blocks. The 3D framework built from the connection of ,-Keggin units by trimesate ions exhibits tunnels filled only by water molecules, which can be partly removed and reintroduced at room temperature. Besides these experimental results, simulation has allowed us to generate two virtual hybrid structures derived from those of known silicates by replacing the Si ions by hypothetical ,-Keggin cations and the O -bridging ligands by terephthalate ions, thus showing that 3D frameworks with large pores can be envisioned in the chemistry of hybrid organic,inorganic materials based on ,-Keggin units and motivating further experimental investigations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Structural Studies on Hydrogen-Bonding Receptors for Barbiturate Guests That Use Metal Ions as Allosteric InhibitorsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 1 2004Mohammad H. Al-Sayah Abstract Receptor 1 was designed to bind barbiturate substrates through a six-point hydrogen-bonding motif only in the absence of metal allosteric cofactors. It was predicted that the binding of metal ions by bipyridine ligands in 1 would result in a geometric change in the receptor to inhibit substrate recognition. However, receptor 1 showed minimal affinity for the barbiturate guests even in the absence of the metal. Binding studies on model compounds 2, 3, 5, and 6 revealed that the inactivity of 1 is due to an intramolecular hydrogen bond between the N,H donor groups and the nitrogen atoms on the first heterocycle of the bipyridine ligands. This intramolecular hydrogen-bonding was eliminated by altering the position of the tether between the bipyridine ligands and the active site to produce receptor 7. Consequently, the high affinity exhibited by 7 for the barbiturate substrate (Ka = 2.8±0.7 × 103M,1 in 9:1 CD2Cl2/CD3CN) was significantly reduced by the addition of ZnII ions as a negative allosteric co-factor. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Tetrakis(,-triisopropylsilanethiolato)-1:2,4S:S;2:3,4S:S -bis(triisopropylsilanethiolato)-1,S,3,S -trizinc(II)ACTA CRYSTALLOGRAPHICA SECTION C, Issue 12 2009Iliana E. Medina-Ramírez The title compound, [Zn3(C9H21SiS)6] or [(iPr3SiS)Zn(,-SSiiPr3)2Zn(,-SSiiPr3)2Zn(SSiiPr3)], is the first structurally characterized homoleptic silanethiolate complex of zinc. A near-linear arrangement of three ZnII ions is observed, the metals at the ends being three-coordinate with one terminally bound silanethiolate ligand. The central ZnII ion is four-coordinate and tetrahedral, with two bridging silanethiolate ligands joining it to each of the two peripheral ZnII ions. The nonbonding intermetallic distances are 3.1344,(11) and 3.2288,(12),Å, while the Zn...Zn...Zn angle is 172.34,(2)°. A trimetallic silanethiolate species of this type has not been previously identified by X-ray crystallography for any element. [source] A novel trinuclear zinc(II) cluster with a tetrahedral ZnO4 coreACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2009Orde Q. Munro The reaction of 0.67 molar equivalents of the O,N,O,-tridentate zwitterionic Schiff base (2Z,4E)-4-[(2-hydroxyphenyl)iminio]pent-2-en-2-olate (H2L) with one equivalent of zinc(II) acetate in methanol affords a novel trinuclear ZnII cluster, di-,-acetato-1:2,2O:O,;2:3,2O:O,-dimethanol-1,O,3,O -bis{,-2-[(2E,3Z)-4-oxidopent-3-en-2-ylideneamino]phenolato}-1:2,4O2,N,O4:O4;2:3,4O4:O2,N,O4 -trizinc(II), [Zn3(C11H11NO2)2(C2H3O2)2(CH4O)2], (I), in which two bridging acetate ligands link the terminal square-based pyramidal ZnII ions to the approximately tetrahedral ZnII ion at the core of the cluster. The ZnO4 coordination group of the central ZnII ion is established by two bridging phenolate and two bridging acetate O atoms. The remaining four coordination sites of each terminal ZnII ion are occupied by methanol and deprotonated H2L. Furthermore, the Zn-bound methanol hydroxyl groups are involved in complementary hydrogen bonding with the Zn-bound enolate O atom of a neighbouring molecule, about an inversion centre in each case. The structure of (I) is therefore best described as an extended one-dimensional hydrogen-bonded chain of trinuclear ZnII clusters. [source] Luminescent Excited-State Intramolecular Proton-Transfer (ESIPT) Dyes Based on 4-Alkyne-Functionalized [2,2,-Bipyridine]-3,3,-diol DyesCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2008Gilles Ulrich Dr. Abstract Functionalized 6,6,-dimethyl-3,3,-dihydroxy-2,2,-bipyridine dyes (BP(OH)2) exhibit relatively intense fluorescence from the relaxed excited state formed by excited-state intramolecular proton transfer (ESIPT). Bromo functionalization of (BP(OH)2) species followed by palladium(0)-catalyzed reactions allows the connection (via alkyne tethers) of functional groups, such as the singlet-emitter diazaboraindacene (bodipy) group or a chelating module (terpyridine; terpy). The X-ray structure of the terpy-based compound confirms the planarity of the 3,3,-dihydroxy-bipyridine unit. The new dyes exhibit relatively intense emission on the nanosecond timescale when in fluid solution, in the solid state at 298,K, and in rigid glasses at 77,K. In some cases, the excitation wavelength luminescence was observed and attributed to 1),inefficiency of the ESIPT process in particular compounds when not enough vibrational energy is introduced in the Franck,Condon state, which is populated by direct light excitation or 2),the presence of an additional excited state that deactivates to the ground state without undergoing the ESIPT process. For some selected species, the effect of the addition of zinc salts on the absorption and luminescence spectra was investigated. In particular, significant fluorescence changes were observed as a consequence of probable consecutive formation of a 1:1 and 1:2 molecular ratio of ligand/zinc adducts owing to coordination of ZnII ions by the bipyridyldiol moieties, except when an additional terpyridine subunit is present. In fact, this latter species preferentially coordinates to the ZnII ion in a 1:1 molecular ratio and further inhibits ZnII interaction. In the hybrid Bodipy/BP(OH)2 species, complete energy transfer from the BP(OH)2 to the bodipy fluorophore occurs, leading to exclusive emission from the lowest-lying bodipy subunit. Des composés colorés à base de 6,6,-dimethyl-3,3,-dihydroxy-2,2,-bipyridine (BP(OH)2) ont été synthétisés et présentent une fluorescence relativement intense issue de la relaxation d,un état excité provenant d,un transfert de proton dans l,état excité (ESIPT). La bromation de dérivés (BP(OH)2) suivie d,un couplage croisé catalysé par du Pd0sous-ligandé permet de connecter (par l,intermédiaire de pont alcyne) des groupes fonctionnels comme un groupe émetteur singulet de type boradiazaindacène (Bodipy) ou un module chélatant universel (une terpyridine). Une structure par diffraction aux rayons X a été obtenu avec le dérivé terpyridine, celle ci confirme la planéité de l,unité 3,3,-dihydroxy-bipyridine. Les nouveaux fluorophores possèdent une émission relativement intense avec une durée de vie de l,ordre de la nanoseconde, en solution et à l,état solide à 298,K ainsi que dans un verre à 77,K. Dans certain cas, la luminescence dépend de la longueur d,onde d,excitation, ce phénomène est attribué à (i) l,inefficacité du processus ESIPT, quand trop peu d,énergie vibrationnelle est introduite dans l,état Franck-Condon peuplé directement par la lumière d,excitation (ii) la présence d,un état excité supplémentaire qui désactive l,état fondamental sans passer par un processus ESIPT. Pour certains composés, l,effet de l,addition de sels de Zinc sur les spectres d,absorption et d,émission a été étudié : en particulier, des changements significatifs de fluorescence ont été observés, probablement due à la formation consécutive de complexes ligand/zinc de st,chiométrie 1:1 et 1:2, provenant de la coordination des cations ZnIIpar l,unité bipyridyl-diol, sauf quand une fonction terpyridine est présente. En fait, dans cette dernière espèce le zinc est préférentiellement coordiné par la terpyridine dans un ratio 1:1, et toute coordination supplémentaire de Zinc semble inhibée. Dans le composé hybride Bodipy/BP(OH)2,un transfert d,énergie quantitatif est observé du BP(OH)2vers le fluorophore Bodipy, entraînant une émission exclusive de la sous-unité Bodipy. Composti basati sulla subunità 6,6,-dimetil-3,3,-dididrossi-2,2,-bipiridina (BP(OH)2), variamente funzionalizzati, presentano fluorescenza relativamente intensa da stati eccitati formati attraverso trasferimento protonico nello stato eccitato (ESIPT). Bromo-funzionalizzazione dei composti di tipo BP(OH)2, seguita da reazioni catalizzate da Pd(0), permettono di connettere (con legame alchinico) gruppi funzionali quali il diazaboroindacene (Bodipy) o un modulo chelante (terpiridina) al frammento BP(OH)2. La struttura ai raggi X del composto contenente la terpiridina conferma la planarità dell,unità 3,3,-diidrossi-bipiridina. Le nuove specie presentano intensa emissione nella scala dei nanosecondi, in soluzione fluida ed allo stato solido a 298,K ed in matrice rigida a 77,K. In alcuni casi, la luminescenza dipende dalla lunghezza d,onda di eccitazione: questo fenomeno è attribuito a (i) inefficienza del processo ESIPT, quando non sufficiente energia vibrazionale è introdotta nello stato Franck-Condon a seguito di eccitazione luminosa o (ii) alla presenza di uno stato eccitato addizionale che si disattiva allo stato fondamentale senza passare dallo stato eccitato prodotto attraverso il meccanismo ESIPT. Per composti selezionati è stato anche studiato l,effetto della presenza di sali di zinco sulle proprietà di assorbimento elettronico e di luminescenza: significativi cambiamenti della fluorescenza sono stati osservati, come conseguenza della consecutiva formazione di addotti 1:1 e 1:2 (rapporto molare BP(OH)2/zinco), dovuta alla coordinazione di cationi di ZnIIda parte del bipiridil-diolo, che si verifica in tutti i casi studiati tranne in presenza di una subunità terpiridinica. In quest,ultimo caso, infatti, si forma soltanto l,addotto 1:1, e ulteriore coordinazione di cationi di ZnIIappare inibita. Nella specie ibrida Bodipy/BP(OH)2si verifica un completo trasferimento di energia elettronica dal BP(OH)2 al Bodipy, che porta ad emissione esclusivamente dalla subunità Bodipy, a piû bassa energia. [source] Ligand Reprogramming in Dinuclear Helicate Complexes: A Consequence of Allosteric or Electrostatic Effects?CHEMISTRY - A EUROPEAN JOURNAL, Issue 18 2007Abstract The ditopic ligand 6,6,-bis(4-methylthiazol-2-yl)-3,3,-([18]crown-6)-2,2,-bipyridine (L1) 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, MeNO2) this ligand forms complexes with ZnII, CdII, HgII and CuI ions via coordination of the N donors to the metal ion. Reaction with both HgII and CuI ions results in the self-assembly of dinuclear double-stranded helicate complexes. The ligands are partitioned by rotation about the central pypy bond, such that each can coordinate to both metals as a bis-bidentate donor ligand. With ZnII ions a single-stranded mononuclear species is formed in which one ligand coordinates the metal ion in a planar tetradentate fashion. Reaction with CdII 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 HgII - or CdII -containing helicate with either Ba2+ or Sr2+ ions effectively reprogrammes the ligand to form only the single-stranded heterobinuclear complexes [MM,(L1)]4+ (M=HgII, CdII; M,=Ba2+, Sr2+), 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 ZnII species, which already exists as a single-stranded mononuclear complex. Similar reactions with the CdII 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 Ba2+ shows that the dinuclear structure still remains intact but the pitch length is significantly increased. [source] | ||||||||||