Cyclic Trinuclear Complexes Research Articles

Revealing High-Lying Intersystem Crossing in Brightly Luminescent Cyclic Trinuclear CuI/AgI Complexes.

The increased attention to luminescent copper(I) complexes, mostly mononuclear and dinuclear ones, in the past few years was mainly due to the new pathways established in the intersystem crossing (ISC) for highly efficient singlet/triplet harvesting, which showed great potential in light-emitting devices. Governing the photophysical processes of planar cyclic trinuclear complexes is more challenging owing to the rich intra- and intermolecular metal-metal interactions involved, but new opportunities also accompany this. Herein reported is a hidden route to the ultra-long-lived, highly efficient phosphorescence of cyclic trinuclear two-coordinate CuI-pyrazolate complexes through pushing the unfavorable metal-to-ligand charge transfer events to the high-lying ISC pathways. Moreover, an anomaly of much higher quantum yields of a trinuclear AgI-pyrazolate complex relative to its CuI analogue is observed.

Unexpected structural transformation into noria-like Ag13 metal clusters and a copper-doping induced boost in photoluminescence.

Polynuclear silver clusters are described that unexpectedly transform from cyclic trinuclear complexes (CTCs) upon reacting with σ-donating phenylacetylene, featuring a noria-like conformation. The introduction of foreign copper ions leads to isomorphic bimetallic Ag/Cu clusters, with a boost in the photoluminescence quantum yield relative to the original silver clusters.

Is a High Photoluminescence Quantum Yield Good Enough for OLEDs? Can Luminescence Rigidochromism Be Manifest in the Solid State? an Optoelectronic Device Screening Case Study for Diphosphine/Pyrazolate Copper(I) Complexes

ABSTRACTThis paper provides a 4th manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry. (For the 1st, 2nd and 3rd manifestations, see: a) Otten, B. M.; Melancon, K. M.; Omary, M. A. “All That Glitters is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers – A Tribute to Al Cotton on the 10th Anniversary of His Passing,” Comments Inorg. Chem. 2018, 38, 1–35; b) Yaseen, W. K.; Sanders, S. F.; Almotawa, R. M.; Otten, B. M.; Bhat, S.; Alamo, D. C.; Marpu, S. B.; Golden, T. D.; Omary, M. A. “Are Metal Complexes “Organic”, “Inorganic”, “Organometallic”, or “Metal-Organic” Materials? A Case Study for the Use of Trinuclear Coinage Metal Complexes as “Metal-Organic Coatings” for Corrosion Suppression on Aluminum Substrates”, Comments Inorg. Chem. 2019, 39, 1–26; and c) Smith, J. B.; Otten, B. M.; Derry, P. J.; Browning, C.; Bodenstedt, K. W.; Sandridge, J. H.; Satumtira, N. T.; Zilaie, M.; Payne, J.; Nuti, R.; Omary, M. A.; Smucker, B. W. “Luminescent, Redox-Active (Dithiolato)Bis(Imine)Platinum(II) Divergent Complexes with Exchangeable Imine Ligands: An Experimental/Computational Study versus Their (Diimine)(Dithiolato)Platinum(II) Convergent Congeners”, Comments Inorg. Chem. 2019, 39, 188–215.) Herein, the dinuclear complexes {Cu[3,5-(CF3)2Pz](µ-dppm)}2 and {Cu[3,5-(CF3)2Pz](µ-dppm)}2•3THF were studied structurally, spectroscopically and via density functional theory (DFT). They were synthesized by reacting bis(diphenylphosphino)methane (dppm) with the cyclic trinuclear complex {μ-[3,5-(CF3)2Pz]Cu}3 to effect nuclearity reduction. Two forms of crystalline solids, {Cu[3,5-(CF3)2Pz](µ-dppm)}2 and {Cu[3,5-(CF3)2Pz](µ-dppm)}2•3THF have been obtained using different recrystallization conditions. The {Cu[3,5-(CF3)2Pz](µ-dppm)}2 complex was found through DFT computations to undergo a distortion from a Y-shaped coordination sphere in the S0 ground state toward a T-shape in the T1 photoexcited, lowest-lying, phosphorescent state. The distortion also causes the copper-copper bond length to contract and form an excimer bond (dCu-Cu = 2.577 Å). Experimentally, the presence of THF in the crystal was found to cause a blue shift, effecting a change in emission color from teal to blue to the naked eye, with a near-unity quantum yields (93%), rendering the latter solid suitable for inorganic LED applications but not OLEDs, as thin films exhibit a reduced quantum yield. Crystallographic evidence suggests that THF leads to a more compact lattice that makes the complexes more rigid and thus hinder the excited state distortions vs unsolvated crystals. Greater distortion leads to a lower energy radiative emission and thus a red shift in the emission color. Films were also studied and found to undergo further red shifting as a result of less rigidity in the media and more surface molecules susceptible to distortion, hence manifesting the luminescence rigidochromism optical phenomenon in the solid state as opposed to the traditional manifestation in frozen vs fluid solution. Photobleaching was studied in both the film and powder to assess photostability, which was superior in neat vs doped solids, which is also favorable for LED applications.

Structures and Photoluminescence of Silver(I) and Gold(I) Cyclic Trinuclear Complexes with Aryl Substituted Pyrazolates

The 4-aryl substituted pyrazolate ligands, L1(Ph)H and L1(Naph)H, were synthesized by Suzuki–Miyaura cross-coupling and combined with metal sources to give cyclic trinuclear structures [AgL1(Ph)]3,...

Ratiometric Phosphorescent Silver Sensor: Detection and Quantification of Free Silver Ions within Silver Nanoparticles.

Silver nanoparticles (AgNPs) have well-known antibacterial properties that have stimulated their widespread production and usage, which nonetheless concomitantly raises concerns regarding their release into the environment. Understanding the toxicity of AgNPs to biological systems, the environment, and the role that each silver species (Ag+ ions vs AgNPs) plays in that toxicity has received significant attention. One of the critical objectives of this research is the development of a reliable method that can sense and differentiate free silver ions from AgNPs and is able to characterize silver ions leaching from nanosilver. A number of analytical methods described in the literature that are available for sensing silver ions are costly, time consuming, tedious, and, more importantly, destroy the AgNP sample. To address these issues, a phosphorescent gold(I)-pyrazolate cyclic trinuclear complex (AuT) known to detect free silver ions was employed to detect and differentiate silver ions from AgNPs within an AgNP sample. The advantage of the proposed silver sensor is its ratiometric emission capability that undermines any background interference. The sensor exhibits a strong red emission (λmax = ∼690 nm) that, in the presence of Ag+ ions, will form a bright-green emissive adduct with a blue-shifted peak maximum near 475 nm yet red-shifted excitation peak. The presence of AgNPs did not inhibit the silver detection and quantification ability of the phosphorescent silver sensor. To understand the chemical transformation of nanosilver, the leaching of silver ions from AgNPs over a period of 35 days was monitored and quantified by measuring the I/ Io changes of the sensor. Furthermore, through adduct formation, the AuT molecular system was able to remediate free silver ions from the solution. The stronger affinity of the AuT complex to "sandwich" free silver ions than AgNPs was demonstrated in the presence of KCl salt that is well documented to form AgCl in the presence of silver ions. To our knowledge, this is the only ratiometric luminescence-based silver sensor able to successfully differentiate between Ag+ ions and AgNPs, sense the silver leakage from AgNPs, and remediate toxic silver ions from an aqueous solution. The synthesis and characterization of this sensor is a simple, single-step process-anticipating its viability for various applications.

Raising the Bar in Aromatic Donor-Acceptor Interactions with Cyclic Trinuclear Gold(I) Complexes as Strong π-Donors.

Aromatic donor-acceptor interactions are of high importance in supramolecular chemistry, materials science and biology. Compared to other noncovalent interactions, such as hydrogen bonding, the binding is often weak. Here we show that strong donor-acceptor interactions between planar aromatics with binding free energies down to -10.1 kcal mol-1 and association constants of up to 2.34 × 107 L mol-1 for 1:1 complexes can be realized using cyclic trinuclear complexes of gold(I) with pyridinate, imidazolate, or carbeniate ligands. Data were obtained through NMR and UV/vis absorption spectroscopic studies and supported by quantum chemical calculations for a variety of acceptors. By using a specifically designed bridged naphthalene diimide-based acceptor with only one binding site, we furthermore show that a 1:2 (donor:acceptor) binding model is best suited to quantify the donor and acceptor/complex equilibrium. Scanning electron microscopy on selected donor-acceptor pairs shows crystalline supramolecular assemblies. We anticipate this study to be relevant for the future design of supramolecular systems and chemical sensors and the determination of binding energies between planar donors and acceptors.

Synthesis, Photophysical Properties, and Computational Analysis of Di- and Tetranuclear Alkyne Complexes of Copper(I) Supported by a Highly Fluorinated Pyrazolate

This work describes the reaction of a cyclic trinuclear complex, {[3,5-(CF3)2Pz]Cu}3, with internal alkynes to construct di- and tetranuclear copper(I) complexes with short cuprophilic contacts and the study of their intriguing bonding and photophysical properties, both experimentally and theoretically. For comparison, we have also investigated the related copper(I) trifluoroacetate 3-hexyne complexes so as to deduce and isolate the role played by the supporting pyrazolate ligand on the luminescence of these and related complexes. Some adducts reported herein feature bridging (i.e., μ2–η2,η2-) alkyne coordination modes, which is rare for copper(I)–alkyne complexes documented in the literature. Raman data show red shifts in the average υC≡C stretching frequency from 2260 cm–1 in free 3-hexyne to 2050 cm–1 in the terminal η2-/2e-donor alkyne adduct Cu2(μ-[3,5-(CF3)2Pz])2(EtC≡CEt)2 (1) and, more drastically, to 1874 cm–1 in the bridged μ2–η2,η2-/4e-donor adduct Cu4(μ-[3,5-(CF3)2Pz])4(μ-EtC≡CEt)2 (2). The te...

Decisive Influence of the Metal in Multifunctional Gold, Silver, and Copper Metallacycles: High Quantum Yield Phosphorescence, Color Switching, and Liquid Crystalline Behavior.

Three cyclic trinuclear pyrazolate complexes with Au(I), Ag(I), or Cu(I) have been studied. These complexes have interesting and distinct optical and thermal properties depending on the metal, namely, liquid crystalline behavior, red or deep-red phosphorescence at room temperature, thermoluminochromism, and response to silver ions. The selected ligand, 4-hexyl-3,5-dimethylpyrazolate, maximizes the effect that the nature of the metals has on the properties of the complexes, thus allowing the intermolecular metallophilic interactions to be responsible for the optical properties. Moreover, the gold and silver complexes show columnar liquid crystal phases at high temperature. All of the complexes have good solubility properties for processing as poly(methyl methacrylate) (PMMA) doped films. Films of the gold, silver, and copper complexes show interesting optical behavior such as wide-range color switching or phosphorescence turn-on upon cooling. In addition, films of the gold complex show a bright color switching (red to blue) in the presence of silver ions. The gold and copper complexes are bright phosphors with phosphorescent quantum yields of 90% in PMMA films, the highest values reported for this class of compounds at room temperature.

A new family of multinuclear mixed-ligand copper(II) clusters: Crystal structures, magnetic properties and catecholase-like activity

In this work we report a family of mixed-ligand copper(II) clusters obtained with different nuclearities: [Cu3(μ-OH)(μ-dppi)3(μ-hfac)3] (1), [Cu4(μ-dppi)4(Hdppi)2(hfac)4] (2), [Cu5(μ-O)2(μ-dppi)(μ-Hdppi)2(μ-hfac)3(hfac)2] (3) and [Cu6(μ-O)2(μ-dppi)2(μ-Hdppi)(μ-hfac)6] (4), where hfac=hexafluoroacetylacetonate, dppi=diphenylphosphinate and Hdppi=diphenylphosphinic acid. Complexes 3 and 4 are the first examples of copper(II) clusters containing a μ-oxo oxygen atom and hfac as bridging ligands. The magnetic properties of all compounds showed predominant antiferromagnetic interactions and the magnetic coupling constants were evaluated using an isotropic exchange model based on the spin topology. A spin frustration phenomena was observed for the equilateral cyclic trinuclear complex (1), thus an antisymmetric exchange term was also considered to fit the experimental magnetic data. The obtained J values are in the range from −89cm−1 to 1.7cm−1 and were interpreted based on structural features. The electrochemical properties and catalytic activity of complexes 1 and 2 were investigated and compared with the [Cu(hfac)2] precursor. Catecholase-like activity of copper(II) complexes via oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylquinone (3,5-DTBQ) was performed.

Variations in binding modes of 2-mercaptobenzoxazolates in the novel cyclic trinuclear complexes [Mn3(CO)10(μ-SCNOC6H4)3] and [Re3(CO)12(μ-SCNOC6H4)3

From reactions of [M2(CO)8(MeCN)2] (MMn, Re) with 2-mercaptobenzoxazol, trinuclear clusters [Mn3(CO)10(μ-SCNOC6H4)3] and [Re3(CO)12(μ-SCNOC6H4)3] have been isolated; the former contains 2-mercaptobenzoxazolate ligands in three different binding modes, while in the latter all three bridge rhenium centres by S,N-coordination, but the three rhenium atoms all have different coordination environments.

Tuning the extended structure and electronic properties of gold(I) thienyl pyrazolates.

A series of thienyl pyrazole proligands and gold(I) thienyl pyrazolate cyclic trinuclear complexes (CTCs) have been synthesized. The relationship between the structure and emission properties of bridging thienyl pyrazolates within gold(I) cyclic trinuclear complexes suggests that the nature of dual emission is sensitive to ligand conjugation length. Density functional theory has been used to support the assignment of metal-sensitized, ligand-localized phosphorescence from monothienyl complexes, while low-lying, ligand-localized LUMOs present in bithienyl systems prohibit metal-sensitized phosphorescence. Soluble n-hexyl derivatives have been synthesized to explore the electrochemical properties of gold(I) thienyl pyrazolates CTCs, and conductive electropolymerized thin films were realized.

Triple‐Decker Au3–Ag–Au3–Ag–Au3 Ion Cluster Enclosed in a Self‐Assembled Cage

Silver in a gold mine: A triple-decker AuI–AgI ion cluster was synthesized by alternate alignment of cyclic trinuclear AuI complexes and AgI ions within a self-assembled cage. The box-shaped cavity of the cage is suitable not only for limiting the cluster number, but also for the stabilization of weakly associated metal ions, which cannot exist without the help of the cage.

Intermolecular aurophilic interactions facilitate assembly of a complex rotaxane in solution

We describe the formation of a complex [2]rotaxane both in solution and in the solid state. The rotaxane ring is composed of a cyclic trinuclear gold complex and the Au(PMe(3))(2)(+) rod is held in place by three aurophilic interactions to the ring Au atoms. The existence of the [2]rotaxane in solution is confirmed by VT-NMR and MS analysis.

Reactivity of mononuclear Pd(ii) and Pt(ii) complexes containing the primary phosphane (ferrocenylmethyl)phosphane towards metal chlorides and PPh3

The reaction of the primary phosphane (ferrocenylmethyl)phosphane [PH(2)CH(2)Fc, ] with an equimolar amount of [M(cod)Cl(2)] (cod = 1,5-cyclooctadiene, M = Pd, Pt) gave the unusual monobridged M(ii) dinuclear complexes of formula [(cod)ClM(micro-PHCH(2)Fc)M(PH(2)CH(2)Fc)Cl(2)] [M = Pt, ; M = Pd, ]. The mechanism leading to and involves the preliminary formation of cis-[M(PH(2)CH(2)Fc)(2)Cl(2)] which further reacts with free [M(cod)Cl(2)] before undergoing dehydrochlorination. The reaction of with PPh(3) led to the unexpected formation of the cyclic trinuclear complex [Pd(3)(micro-PHCH(2)Fc)(3)(PPh(3))(2)(PH(2)CH(2)Fc)Cl(3)] (). Further reaction of with PPh(3) led to the substitution of the tertiary phosphane for the primary one with formation of two geometric isomers and of formula [Pd(micro-PHCH(2)Fc)(PPh(3))Cl](3) differing only for the position of the PPh(3) group replacing the PH(2)CH(2)Fc ligand. In complex each micro-PHCH(2)Fc group bridging two palladium atoms has a terminal PPh(3) ligand in trans position with respect to the first Pd (the cis position being occupied by a chlorine) and a chlorine ligand trans to the other Pd (the cis position being occupied by a terminal PPh(3) ligand) thus rendering chemically equivalent the three PPh(3) (and the three phosphides). In complex the three terminal PPh(3) as well as the three bridging phosphido ligands are chemically inequivalent. Complexes and coexist in equilibrium in solution, but only precipitates from CH(2)Cl(2)-n-hexane yielding crystals suitable for X-ray analyses. These crystals are water/n-hexane solvates and belong to the monoclinic space P2(1)/c with a = 25.063(6) A, b = 15.564(4) A, c = 26.089(5) A, beta = 120.017(16) degrees . They contain two identical couples of enantiomers of . The peculiar arrangement of three metals and three phosphorus atoms of the bridging ligands ascertained for trimers , and has no precedent in the rich class of palladium and platinum phosphido chemistry.

Catalytic decomposition of dimethyldioxirane and cyclic acetone triperoxide in presence of polynuclear complexes of cobalt(II,III) and copper(II)

Dinuclear copper and cyclic trinuclear cobalt complexes with pyrazolate and OH − bridges are able to decompose dimethyldioxirane in acetone, triggering radical reactions. Some products of reactions between organic substrates (cyclohexene or ethylbenzene) or acetone with secondary radicals formed from dimethyldioxirane: hydroxyl, methyl and acetomethyl, were identified and quantified. Tested complexes were also able to homolytically decompose cyclic acetone triperoxide and the radicals formed induced homolytic oxidation of cyclohexene producing 2-cyclohexen-1-ol and 2-cyclohexen-1-one at moderate yield.

Cyclic Trimer versus Head−Tail Dimer in Metal−Nucleobase Complexes: Importance of Relative Orientation (Syn, Anti) of the Metal Entities and Relevance as a Metallaazacrown Compound

The formation and crystal structure analysis of a cyclic trinuclear Pd complex with bridging 1-methylcytosinato model nucleobases is reported: [[(tmeda)Pd(1-MeC(-)-N3,N4)]3] (ClO4)3.5.5H2O (tmeda = N,N,N',N'-tetramethylethylenediamine; 1-MeC- = 1-methylcytosine deprotonated at exocyclic amino group) is obtained, among others, from the hydroxo-bridged dinuclear species [[(tmeda)Pd(OH)]2](ClO4)2, which likewise has been characterized by X-ray crystallography, and 1-MeC (1-MeC = neutral 1-methylcytosine) in aqueous solution. The usual head-tail dimer (HT1) appears not to be formed presumably because of the steric bulk of the tmeda ligand, which prevents a close approach of two tmeda ligands. There is also no evidence for formation of an alternative head-tail dimer structure (HT2) which, in principle, would not lead to any steric clash of ligands, but would require an orientation of the metal at N4 that is almost perpendicular to the nucleobase plane. In the Pd3 compound, the bridging metals are approximately in an anti arrangement, thereby leading to Pd...Pd separations within the Pd3 triangle close to 5.2 angstroms. This arrangement is reflected in the 1H NMR spectrum by a strongly deshielded H5 resonance of the nucleobase, occurring at 6.56 ppm (D2O). The overall structure of the Pd3 is that of a double cone, with ClO4- counterions approaching the cavities from either side. The trinuclear structure is also maintained in Me2SO-d6. In this solvent, Pd3 acts as a fluoride anion receptor, with F- binding to the N4H protons, as evident from large downfield shifts of these protons. The compound is compared with cyclic adeninato complexes of hexacoordinated metal ions, and a conceptional analogy with [12]metallacrown-3 species is outlined.

Metal Effect on the Supramolecular Structure, Photophysics, and Acid−Base Character of Trinuclear Pyrazolato Coinage Metal Complexes

Varying the coinage metal in cyclic trinuclear pyrazolate complexes is found to significantly affect the solid-state packing, photophysics, and acid-base properties. The three isoleptic compounds used in this study are [[3,5-(CF3)2Pz]M]3 with M = Cu, Ag, and Au (i.e., Cu3, Ag3, and Au3, respectively). They form isomorphous crystals and exist as trimers featuring nine-membered M3N6 rings with linear two-coordinate metal sites. On the basis of the M-N distances, the covalent radii of two-coordinate Cu(I), Ag(I), and Au(I) were estimated as 1.11, 1.34, and 1.25 angstroms, respectively. The cyclic [[3,5-(CF3)2Pz]M]3 complexes pack as infinite chains of trimers with a greater number of pairwise intertrimer M...M interactions upon proceeding to heavier coinage metals. However, the intertrimer distances are conspicuously short in Ag3 (3.204 angstroms) versus Au3 (3.885 angstroms) or Cu3 (3.813 angstroms) despite the significantly larger covalent radius of Ag(I). Remarkable luminescence properties are found for the three M3 complexes, as manifested by the appearance of multiple unstructured phosphorescence bands whose colors and lifetimes change qualitatively upon varying the coinage metal and temperature. The multiple emissions are assigned to different phosphorescent excimeric states that exhibit enhanced M...M bonding relative to the ground state. The startling luminescence thermochromic changes in crystals of each compound are related to relaxation between the different phosphorescent excimers. The trend in the lowest energy phosphorescence band follows the relative triplet energy of the three M(I) atomic ions. DFT calculations indicate that [[3,5-(R)2Pz]M]3 trimers with R = H or Me are bases with the relative basicity order Ag << Cu < Au while fluorination (R = CF3) renders even the Au trimer acidic. These predictions were substantiated experimentally by the isolation of the first acid-base adduct, [[Au3]2:toluene]infinity, in which a trinuclear Au(I) complex acts as an acid.

Gold(III) Phenylphosphides and -phosphodiides

In this paper we describe the synthesis of a series of cyclic and acyclic gold phosphine, phosphide, and phosphodiide derivatives of the primary phosphine PPhH2. Thus, by reacting [Au(C6F5)x(tht)] (x = 1, 3) with an equimolecular amount of PPhH2, the phosphino complexes [Au(C6F5)x(PPhH2)] (x = 1, 3) are obtained. The gold(III) complex [Au(C6F5)3(PPhH2)] reacts with gold(I), silver(I), or gold(III) reagents in the presence of a deprotonating agent, leading to the new di- or trinuclear phenylphosphide derivatives [Au(C6F5)3(μ-PPhH)Au(PR3)] (R = Ph, Me), PPN[{Au(C6F5)3}2(μ-PPhH)], or PPN[{Au(C6F5)3(μ-PPhH)}2M] (M = Au, Ag). The anionic gold(III) complex PPN[{Au(C6F5)3}2(μ-PPhH)] further reacts with similar gold(I) precursors to afford higher nuclearity phosphodiide species, such as PPN[{Au(C6F5)3}2(μ3-PPh){Au(PPh3)}], (PPN)2[{Au(C6F5)3}2(μ3-PPh){Au(C6F5)}], or (PPN)3[{(Au(C6F5)3)2(μ3-PPh)}2Au]. Furthermore, treatment of [Au(C6F5)2(μ-Cl)]2 with PPhH2 results in the formation of the cyclic trinuclear complex [...

Pyrazolato-bridged polynuclear palladium and platinum complexes. Synthesis, structure, and reactivity.

Cyclic trinuclear complexes [Pd(3)(mu-pz)(6)] (1) and [Pd(3)(mu-4-Mepz)(6)] (2) and dinuclear complex [Pd(2)(mu-3-t-Bupz)(2)(3-t-Bupz)(2)(3-t-BupzH)(2)] (3) have been prepared by the reactions of [PdCl(2)(CH(3)CN)(2)] with pyrazole (pzH), 4-methylpyrazole (4-MepzH), and 3-tert-butylpyrazole (3-t-BupzH), respectively, in CH(3)CN in the presence of Et(3)N. In the absence of the base, treatment of [PdCl(2)(CH(3)CN)(2)] with pzH gave the mononuclear complex, [Pd(pzH)(4)]Cl(2) (6). The reaction of [PtCl(2)(C(2)H(5)CN)(2)] with pzH in the presence of Et(3)N under refluxing in C(2)H(5)CN afforded the known dimeric Pt(II) complex, [Pt(pz)(2)(pzH)(2)](2) (7). The protons participating in the hydrogen bonding in 3 and 7 are easily replaced by silver ions to give the heterotetranuclear complex [Pd(2)Ag(2)(mu-3-t-Bupz)(6)] (4) and the heterohexanuclear complex [Pt(2)Ag(4)(mu-pz)(8)] (5). The complexes 1-6 are structurally characterized.

Diastereomeric separations and crystal structures of rhodium(iii) and iridium(iii) complexes containing adenosine and related nucleosidesElectronic supplementary information (ESI) available: 1H NMR and CD spectra. See http://www.rsc.org/suppdata/dt/b2/b209148h/

Six C3 cyclic trinuclear complexes [{M(Cp*)(L)}3]3+ (M = RhIII and IrIII; Cp* = η5–C5Me5) containing adenosine nucleosides [L: adenosine (Hado), 2′-deoxyadenosine (Hdeoado) and 5′-acetyl-2′,3′-isopropylideneadenosine (Haipado)] were prepared and characterized by UV/Vis and circular dichroism (CD) spectra, NMR spectroscopy, electrospray ionization mass spectroscopy and X-ray crystal structure analysis. The isolations of one and/or two diastereomers were successfully carried out for the four systems by second-order asymmetric transformation and/or fractional crystallization. Interestingly, a striking kinetic difference was found between the present RhIII– and IrIII–ado systems. The crystal structure of CCC-[{Rh(Cp*)(ado)}3](CF3SO3)3·2.5H2O·CH3OH revealed that the ado ligand adopts a μ-1κN1:2κ2N6,N7 bridging mode and the three purine rings forming a triangle dome-like cavity can include one methanol molecule into its cavity. The absolute configurations were assigned to these complexes based on the crystal structural result and CD spectral arguments. The RhIII–N-methyl adenosine (HNMeado) system exceptionally gave a di-μ-hydroxy anti-dinuclear structure because of the weak coordination ability of the N(6) donor.