Controlling the Photophysical Properties of a Series of Isostructural d6 Complexes Based on Cr0, MnI, and FeII.

Development of first-row transition metal complexes with similar luminescence and photoredox properties as widely used RuII polypyridines is attractive because metals from the first transition series are comparatively abundant and inexpensive. The weaker ligand field experienced by the valence d-electrons of first-row transition metals challenges the installation of the same types of metal-to-ligand charge transfer (MLCT) excited states as in precious metal complexes, due to rapid population of energetically lower-lying metal-centered (MC) states. In a family of isostructural tris(diisocyanide) complexes of the 3d6 metals Cr0, MnI, and FeII, the increasing effective nuclear charge and ligand field strength allow us to control the energetic order between the 3MLCT and 3MC states, whereas pyrene decoration of the isocyanide ligand framework provides control over intraligand (ILPyr) states. The chromium(0) complex shows red 3MLCT phosphorescence because all other excited states are higher in energy. In the manganese(I) complex, a microsecond-lived dark 3ILPyr state, reminiscent of the types of electronic states encountered in many polyaromatic hydrocarbon compounds, is the lowest and becomes photoactive. In the iron(II) complex, the lowest MLCT state has shifted to so much higher energy that 1ILPyr fluorescence occurs, in parallel to other excited-state deactivation pathways. Our combined synthetic-spectroscopic-theoretical study provides unprecedented insights into how effective nuclear charge, ligand field strength, and ligand π-conjugation affect the energetic order between MLCT and ligand-based excited states, and under what circumstances these individual states become luminescent and exploitable in photochemistry. Such insights are the key to further developments of luminescent and photoredox-active first-row transition metal complexes.

First-Row d6 Metal Complex Enables Photon Upconversion and Initiates Blue Light-Dependent Polymerization with Red Light.

Photosensitizers for sensitized triplet-triplet annihilation upconversion (sTTA-UC) often rely on precious heavy metals, whereas coordination complexes based on abundant first-row transition metals are less common. This is mainly because long-lived triplet excited states are more difficult to obtain for 3d metals, particularly when the d-subshell is only partially filled. Here, we report the first example of sTTA-UC based on a 3d6 metal photosensitizer yielding an upconversion performance competitive with precious metal-based analogues. Using a newly developed Cr0 photosensitizer featuring equally good photophysical properties as an OsII benchmark complex in combination with an acetylene-decorated anthracene annihilator, red-to-blue upconversion is achievable. The upconversion efficiency under optimized conditions is 1.8 %, and the excitation power density threshold to reach the strong annihilation limit is 5.9 W/cm2 . These performance factors, along with high photostability, permit the initiation of acrylamide polymerization by red light, based on radiative energy transfer between delayed annihilator fluorescence and a blue light absorbing photo-initiator. Our study provides the proof-of-concept for photon upconversion with elusive first-row analogues of widely employed precious d6 metal photosensitizers, and for their application in photochemical reactions triggered by excitation wavelengths close to near-infrared.

Photoredox-active Cr(0) luminophores featuring photophysical properties competitive with Ru(II) and Os(II) complexes.

Coordination complexes of precious metals with the d6 valence electron configuration such as Ru(II), Os(II) and Ir(III) are used for lighting applications, solar energy conversion and photocatalysis. Until now, d6 complexes made from abundant first-row transition metals with competitive photophysical and photochemical properties have been elusive. While previous research efforts focused mostly on Fe(II), we disclose that isoelectronic Cr(0) gives access to higher photoluminescence quantum yields and excited-state lifetimes when compared with any other first-row d6 metal complex reported so far. The luminescence behaviour of the metal-to-ligand charge transfer excited states of these Cr(0) complexes is competitive with Os(II) polypyridines. With these Cr(0) complexes, the metal-to-ligand charge transfer states of first-row d6 metal complexes become exploitable in photoredox catalysis, and benchmark chemical reductions proceed efficiently under low-energy red illumination. Here we demonstrate that appropriate molecular design strategies open up new perspectives for photophysics and photochemistry with abundant first-row d6 metals.

Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds.

Many organometallic iridium(III) complexes have photoactive excited states with mixed metal-to-ligand and intraligand charge transfer (MLCT/ILCT) character, which form the basis for numerous applications in photophysics and photochemistry. Cobalt(III) complexes with analogous MLCT excited-state properties seem to be unknown yet, despite the fact that iridium(III) and cobalt(III) can adopt identical low-spin d6 valence electron configurations due to their close chemical relationship. Using a rigid tridentate chelate ligand (LCNC), in which a central amido π-donor is flanked by two σ-donating N-heterocyclic carbene subunits, we obtained a robust homoleptic complex [Co(LCNC)2](PF6), featuring a photoactive excited state with substantial MLCT character. Compared to the vast majority of isoelectronic iron(II) complexes, the MLCT state of [Co(LCNC)2](PF6) is long-lived because it does not deactivate as efficiently into lower-lying metal-centered excited states; furthermore, it engages directly in photoinduced electron transfer reactions. The comparison with [Fe(LCNC)2](PF6), as well as structural, electrochemical, and UV-vis transient absorption studies, provides insight into new ligand design principles for first-row transition-metal complexes with photophysical and photochemical properties reminiscent of those known from the platinum group metals.

Magnetic-Field Universality of the Kondo Effect Revealed by Thermocurrent Spectroscopy.

Probing the universal low-temperature magnetic-field scaling of Kondo-correlated quantum dots via electrical conductance has proved to be experimentally challenging. Here, we show how to probe this in nonlinear thermocurrent spectroscopy applied to a molecular quantum dot in the Kondo regime. Our results demonstrate that the bias-dependent thermocurrent is a sensitive probe of universal Kondo physics, directly measures the splitting of the Kondo resonance in a magnetic field, and opens up possibilities for investigating nanosystems far from thermal and electrical equilibrium.

The surprising effects of sulfur: achieving long excited-state lifetimes in heteroleptic copper(i) emitters.

A series of heteroleptic [Cu(N^N)(P^P)][PF6] complexes is reported in which N^N is a di(methylsulfanyl)-1,10-phenanthroline (2,9-, 3,8- or 4,7-(MeS)2phen) or di(methoxy)-1,10-phenanthroline (2,9-, 3,8- or 4,7-(MeO)2phen) and P^P is bis(2-(diphenylphosphano)phenyl)ether (POP) or 4,5-bis(diphenylphosphano)-9,9-dimethylxanthene (xantphos). The effects of the different substituents are investigated through structural, electrochemical and photophysical studies and by using DFT and TD-DFT calculations. Introducing methylsulfanyl groups in the 2,9-, 3,8- or 4,7-positions of the phen domain alters the composition of the frontier molecular orbitals of the [Cu(N^N)(P^P)]+ complexes significantly, so that ligand-centred (LC) transitions become photophysically relevant with respect to metal-to-ligand charge transfer (MLCT). Within this series, [Cu(2,9-(MeS)2phen)(POP)][PF6] exhibits the highest photoluminescence quantum yield of 15% and the longest excited-state lifetime of 8.3 µs in solution. In the solid state and in frozen matrices at 77 K, the electronic effects of the methylsulfanyl or methoxy substituents are highlighted, thus resulting in luminescence lifetimes of 2 to 4.2 ms at 77 K with predominantly LC character for both the 3,8- and 4,7-(MeS)2phen containing complexes. The results of the investigation give new guidelines on how to influence the luminescence properties in [Cu(N^N)(P^P)]+ complexes which will aid in the development of new sustainable and efficient copper(i) emitters.

Luminescent chromium(0) and manganese(I) complexes.

In this Frontier article, recently discovered chromium(0) and manganese(I) complexes emitting from metal-to-ligand charge transfer (MLCT) excited states are highlighted. Chelating isocyanide ligands give access to this new class of 3d6 emitters with MLCT lifetimes in (or close to) the nanosecond regime in solution at room temperature. Although the so far achievable luminescence quantum yields in these open-shell complexes are yet comparatively low, the photophysical properties of the new chromium(0) and manganese(I) isocyanides are reminiscent of those of well-known ruthenium(II) polypyridines. Our findings provide insight into how undesired nonradiative MLCT deactivation in 3d6 complexes can be counteracted, and they seem therefore relevant for the further development of new luminescent first-row transition metal complexes based on iron(II) and cobalt(III) in addition to chromium(0) and manganese(I).

Luminescent First-Row Transition Metal Complexes.

Precious and rare elements have traditionally dominated inorganic photophysics and photochemistry, but now we are witnessing a paradigm shift toward cheaper and more abundant metals. Even though emissive complexes based on selected first-row transition metals have long been known, recent conceptual breakthroughs revealed that a much broader range of elements in different oxidation states are useable for this purpose. Coordination compounds of V, Cr, Mn, Fe, Co, Ni, and Cu now show electronically excited states with unexpected reactivity and photoluminescence behavior. Aside from providing a compact survey of the recent conceptual key advances in this dynamic field, our Perspective identifies the main design strategies that enabled the discovery of fundamentally new types of 3d-metal-based luminophores and photosensitizers operating in solution at room temperature.

Controlling the Entropy of a Single-Molecule Junction.

Single molecules are nanoscale thermodynamic systems with few degrees of freedom. Thus, the knowledge of their entropy can reveal the presence of microscopic electron transfer dynamics that are difficult to observe otherwise. Here, we apply thermocurrent spectroscopy to directly measure the entropy of a single free radical molecule in a magnetic field. Our results allow us to uncover the presence of a singlet to triplet transition in one of the redox states of the molecule, not detected by conventional charge transport measurements. This highlights the power of thermoelectric measurements which can be used to determine the difference in configurational entropy between the redox states of a nanoscale system involved in conductance without any prior assumptions about its structure or microscopic dynamics.

Pyrene-Decoration of a Chromium(0) Tris(diisocyanide) Enhances Excited State Delocalization: A Strategy to Improve the Photoluminescence of 3d6 Metal Complexes.

There is a long-standing interest in iron(II) complexes that emit from metal-to-ligand charge transfer (MLCT) excited states, analogous to ruthenium(II) polypyridines. The 3d6 electrons of iron(II) are exposed to a relatively weak ligand field, rendering nonradiative relaxation of MLCT states via metal-centered excited states undesirably efficient. For isoelectronic chromium(0), chelating diisocyanide ligands recently provided access to very weak MLCT emission in solution at room temperature. Here, we present a concept that boosts the luminescence quantum yield of a chromium(0) isocyanide complex by nearly 2 orders of magnitude, accompanied by a significant increase of the MLCT lifetime. Pyrene units in the diisocyanide ligand backbone lead to an enlarged π-conjugation system and to a strongly delocalized MLCT state, from which nonradiative relaxation is less dominant despite a sizable redshift of the emission. While the pyrene moiety is electronically coupled to the core of the chromium(0) complex in the excited state, UV-vis absorption and 2D NMR spectroscopy show that this is not the case in the ground state. Luminescence lifetimes and quantum yields for our pyrenyl-decorated chromium(0) complex exhibit an unusual bell-shaped dependence on solvent polarity, indicative of two counteracting effects governing the MLCT deactivation. These two effects are identified as predominant deactivation either through an energetically nearby lying metal-centered state in the most apolar solvents, or alternatively via direct nonradiative relaxation to the ground state following the energy gap law in more polar solvents. This is the first example of a 3d6 MLCT emitter to benefit from an increased π-conjugation network.

Cooperative Co-Activation of Water and Hypochlorite by a Non-Heme Diiron(III) Complex.

Aqueous solutions of the iron(III) complex of N,N,N'-tris(2-pyridylmethyl)ethylenediamine-N'-acetate (tpena) react with hypochlorite (ClO-) to produce the reactive high-valent [FeIV(O)(tpena)]+. Under catalytic conditions, in bicarbonate-buffered media (pH 8) with a set ionic strength (10 mM NaCl), kinetic analysis shows that two equivalents of [FeIV(O)(tpena)]+ per one ClO- are produced, with benign chloride ions the only byproduct. An unprecedented supramolecular activation of ClO- by {(HCO3)⊂[(tpena)FeIII(µ-O)FeIII(Htpena)]}2+ is proposed. This mode of activation has great advantage for use in the catalytic oxidation of C-H bonds in water since: (i) the catalyst scaffold is protected from oxidative degradation and (ii) undesirable radical side reactions which produce toxic chlorinated compounds are circumvented by this novel coactivation of water and ClO-. The unique activation mechanism by the Fe-tpena system makes possible the destruction of organic contaminants as an add-on technology to water disinfection by chlorination, demonstrated here through (i) the catalytic oxidation of micropollutant metaldehyde, and (ii) mineralization of the model substrate formate. The resting-state speciation at pH 3, 5, 7, and 9, as well as the catalytically active iron speciation are characterized with Mössbauer and EPR spectroscopy and supported by DFT calculations. Our study provides fundamentally new insights into the design and activation mode of iron-based catalysts relevant to applications in water remediation.

Engineering the Oxidative Potency of Non-Heme Iron(IV) Oxo Complexes in Water for C-H Oxidation by a cis Donor and Variation of the Second Coordination Sphere.

A series of iron(IV) oxo complexes, which differ in the donor (CH2py or CH2COO-) cis to the oxo group, three with hemilabile pendant donor/second coordination sphere base/acid arms (pyH/py or ROH), have been prepared in water at pH 2 and 7. The νFe═O values of 832 ± 2 cm-1 indicate similar FeIV═O bond strengths; however, different reactivities toward C-H substrates in water are observed. HAT occurs at rates that differ by 1 order of magnitude with nonclassical KIEs (kH/kD = 30-66) consistent with hydrogen atom tunneling. Higher KIEs correlate with faster reaction rates as well as a greater thermodynamic stability of the iron(III) resting states. A doubling in rate from pH 7 to pH 2 for substrate C-H oxidation by the most potent complex, that with a cis-carboxylate donor, [FeIVO(Htpena)]2+, is observed. Supramolecular assistance by the first and second coordination spheres in activating the substrate is proposed. The lifetime of this complex in the absence of a C-H substrate is the shortest (at pH 2, 3 h vs up to 1.3 days for the most stable complex), implying that slow water oxidation is a competing background reaction. The iron(IV)═O complex bearing an alcohol moiety in the second coordination sphere displays significantly shorter lifetimes due to a competing selective intramolecular oxidation of the ligand.

Photosynthesis of a Dihydroimidazopyridine Chelate Shines Light on the Reactions of a Photoactivated Iron(III) Complex with O2.

The high-spin (S = 5/2) meridional diastereoisomer of [FeIII(tpena)]2+ (tpena = N,N,N'-tris(2-pyridylmethyl)ethylendiamine-N'-acetate), mer-[Fe(tpena)]2+, undergoes photolytic CO2 release to produce an iron(II) intermediate of a radical dihydroimidazopyridine ligand (L•). The structure of this unprecedented transient iron(II)(L•) complex is supported by UV-vis and Mössbauer spectroscopies, DFT calculations, as well as the X-ray structural characterization of an µ-oxo iron(III) complex of the oxidized derivative of L•, namely, [FeIII2O(Cl)2(L+)2](ClO4)4(MeCN)2 (L+ = 2-(2-(bis(pyridin-2-ylmethyl)amino)ethyl)-2,3-dihydro-1H-imidazo[1,5-a]pyridin-4-ium). [FeIII2O(Cl)2(L+)2]4+ is obtained only in the absence of O2. Under aerobic conditions, O2 will intercept the iron(II)(L•) complex to form a putative Fe(III)-alkylperoxide complex which cascades to an iron(II) complex of SBPy3 (SBPy3 = N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2-aldimine). Thus, through different oxidative pathways, the unknown ligand L+ or SBPy3 forms by loss of a one-carbon-atom or a two-carbon-atom unit, respectively, from the glycyl arm of tpena. Acceleration of the photodecarboxylation step is achieved by addition of thiocyanate because of transient formation of a more photoreactive NCS- adduct of [Fe(tpena)]2+. This has allowed for kinetic observation of the reaction of [FeII(L•)]2+ with O2 which is, unexpectedly, promoted also by light. We propose that this corresponds to the energy needed for the conversion of the ring-closed radical ligand L• to a ring-opened tautomer to allow for O2 insertion between the C and Fe atoms of the iron(II) complex.

cis Donor Influence on O-O Bond Lability in Iron(III) Hydroperoxo Complexes: Oxidation Catalysis and Ligand Transformation.

The FeIII/FeII redox potentials for [Fe(tpen)]2+/3+, [Fe(tpena)]+/2+, and [Fe(tpenO)]+/2+ (N-R-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine, where R = CH2C6H4N, CH2COO-, CH2CH2O-, respectively) span 470 mV with the oxidation potentials following the order [FeII(tpenO)]+ (MeOH) < [FeII(tpena)]+ (MeCN) < [FeII(tpen)]2+ (MeCN). In their +3 oxidation states the complexes react with 1 equiv of H2O2 to give the purple [FeIII(OOH)(HL)]n+ (n = 2 for L = tpena, tpenO; n = 3 for L = tpen). A pyridine arm is decoordinated in these complexes, furnishing a second coordination sphere base which is protonated at ambient pH. The lifetimes of these transient species depend on how readily the substrate (sometimes the solvent) is oxidized and reflect the trend in both the O-O bond lability and oxidizing potency of the putative iron-based oxidant derived from the iron(III) peroxides. In methanol solution, [FeIII(tpenO)]2+ and [FeIII(tpena)]2+ exist in their Fe(III) states and hence the formation of [FeIII(OOH)(Htpena)]2+ and [FeIII(OOH)(HtpenO)]2+ is instantaneous. This is in contrast to the short lag time that occurs before adduct formation between [FeII(tpen)]2+ and H2O2 due to the requisite prior oxidation of the solution-state iron(II) complex to its iron(III) state. Stabilization of the +3 iron oxidation state in the resting state catalysts affords complexes that activate H2O2 more readily with the consequence of higher yields in the oxidation of the C-H bonds using H2O2 as terminal oxidant. The presence of a cis monodentate carboxylato donor increases the rate of oxidation by hydrogen atom transfer in comparison to the systems with an alkoxo or pyridine in this position. Competing with substrate oxidation is the oxidative modification of the alkoxido group in [FeIII(tpenO)]2+, converting it to a carboxylato group in the presence of H2O2: in effect, transforming tpenO to tpena.

Photoinduced O2-Dependent Stepwise Oxidative Deglycination of a Nonheme Iron(III) Complex.

The iron(III) complex [Fe(tpena)]2+ (tpena = N, N, N'-tris(2-pyridylmethyl)ethylendiamine- N'-acetate) undergoes irreversible O2-dependent N-demethylcarboxylation to afford [FeII(SBPy3)(MeCN)]2+ (SBPy3 = N, N-bis(2-pyridylmethyl)amine- N-ethyl-2-pyridine-2-aldimine), when irradiated with near-UV light. The loss of a mass equivalent to the glycyl group in a process involving consecutive C-C and C-N cleavages is documented by the measurement of the sequential production of CO2 and formaldehyde, respectively. Time-resolved UV-vis absorption, Mössbauer, EPR, and Raman spectroscopy have allowed the spectroscopic characterization of two iron-based intermediates along the pathway. The first of these, proposed to be a low-spin iron(II)-radical ligand complex, reacts with O2 in the rate-determining step to produce a putative alkylperoxide complex. DFT calculations suggest that this evolves into an Fe(IV)-oxo species, which can abstract a hydrogen atom from a cis methylene group of the ligand to give the second spectroscopically identified intermediate, a high-spin iron(III)-hydroxide of the product oxidized ligand, [FeIII(OH)(SBPy3)]2+. Reduction and exchange of the cohydroxo/water ligand produces the crystallographically characterized products [FeII(SBPy3)(X)]2+/3+, X = MeCN, [Zn(tpena)]+.

Novel conformationally constrained 2'-C-methylribonucleosides: synthesis and incorporation into oligonucleotides.

Synthesis of two novel conformationally constrained bicyclic ribonucleoside phosphoramidites bearing a 2'-C-methyl substituent has been accomplished. These phosphoramidites were used to incorporate the corresponding 2'-C-methyl nucleotides into oligonucleotides and to study their effects on duplex thermal stability. Whereas the C2'-O4'-linked LNA-type derivative induced severe destabilization of duplexes formed with complementary DNA and RNA, the C3'-O4'-linked derivative induced RNA-selective hybridization with increased affinity relative to that of the unmodified DNA-based probe.

Directing a Non-Heme Iron(III)-Hydroperoxide Species on a Trifurcated Reactivity Pathway.

The reactivity of [FeIII (tpena)]2+ (tpena=N,N,N'-tris(2-pyridylmethyl)ethylenediamine-N'-acetate) as a catalyst for oxidation reactions depends on its ratio to the terminal oxidant H2 O2 and presence or absence of sacrificial substrates. The outcome can be switched between: 1) catalysed H2 O2 disproportionation, 2) selective catalytic oxidation of methanol or benzyl alcohol to the corresponding aldehyde, or 3) oxidative decomposition of the tpena ligand. A common mechanism is proposed involving homolytic O-O cleavage in the detected transient purple low-spin (S=1/2 ) [(tpenaH)FeIII O-OH]2+ . The resultant iron(IV) oxo and hydroxyl radical both participate in controllable hydrogen-atom transfer (HAT) reactions. Consistent with the presence of a weaker σ-donor carboxylate ligand, the most pronounced difference in the spectroscopic properties of [Fe(OOH)(tpenaH)]2+ and its conjugate base, [Fe(OO)(tpenaH)]+ , compared to non-heme iron(III) peroxide analogues supported by neutral multidentate N-only ligands, are slightly blue-shifted maxima of the visible absorption band assigned to ligand-to-metal charge-transfer (LMCT) transitions and, corroborating this, lower FeIII /FeII redox potentials for the pro-catalysts.

Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering.

Gas-phase clustering of nonionizable iodylbenzene (PhIO2) is attributed to supramolecular halogen bonding. Electrospray ionization results in the formation of ions of proton-charged and preferably sodium-charged clusters assignable to [H(PhIO2) n ]+, n = 1-7; [Na(PhIO2) n ]+, n = 1-6; [Na2(PhIO2) n ]2+, n = 7-20; [HNa(PhIO2) n ]2+, n = 6-19; [HNa2(PhIO2) n ]3+, n = 15-30; and [Na3(PhIO2) n ]3+, n = 14-30. The largest cluster detected has a supramolecular mass of 7147 Da. Electronic structure calculations using the M06-2X functional with the 6-311++G(d,p) basis set for C, H, and O, and LANL2DZ basis set for I and Na predict 298 K binding enthalpies for the protonated and sodiated iodylbenzene dimers and trimers are greater than 180 kJ/mol. This is exceptionally high in comparison with other protonated and sodiated clusters with well-established binding enthalpies. Strongly halogen-bonded motifs found in the crystalline phases of PhIO2 and its derivatives serve as models for the structures of larger gas-phase clusters, and calculations on simple model gas-phase dimer and trimer clusters result in similar motifs. This is the first account of halogen bonding playing an extensive role in gas-phase associations. Graphical Abstract ᅟ.

Reduction of hypervalent iodine by coordination to iron(iii) and the crystal structures of PhIO and PhIO2.

The iodine L3-edge X-ray Absorption Near Edge Structure (XANES) of organic and inorganic iodine compounds with formal iodine oxidation states ranging from -1 to +7 shows edge energies spanning from 4560.8 eV to 4572.5 eV. These were used to calibrate the oxidation state of iodine in a unique iron complex of iodosylbenzene (PhIO), [Fe(tpena)OIPh]2+ (tpena- = N,N,N'-tris(2-pyridylmethyl)ethylenediamine-N'-acetate), which was found to be +1.6. Thus the iodine oxidation state is reduced by 1.4 compared with that in precursor uncoordinated PhIO. On the basis of a combination of X-ray diffraction and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, we have determined the unknown crystal structure of PhIO, along with a new phase of iodylbenzene (ß-PhIO2) using the Rietveld method. Analogous 1-D chains of halogen bonded [O-IO-I] motifs are the dominant supramolecular interactions between PhIO and PhIO2 monomers in each structure respectively and the polymeric structures rationalise the general insolubility of these oxygen atom transfer reagents. A double stack of phenyl units in PhIO is found between the layers of the halogen bonded O/I chains. In the case of PhIO, C-Hπ interactions between adjacent phenyl groups result in the alternate phenyl groups lying in parallel planes. Supplementing the strong polymerizing halogen bonds, this supramolecular interaction must exacerbate the insolubility of PhIO. The pillared structure of the new rhombohedral ß-PhIO2 differs significantly from the known monoclinic lamellar phase, α-PhIO2, described 36 years ago in which the chains form lamellar stacks [N. W. Alcock and J. F. Sawyer, J. Chem. Soc., Dalton Trans., 1980, 115-120].

A coordinatively flexible hexadentate ligand gives structurally isomeric complexes M2(L)X3 (M = Cu, Zn; X = Br, Cl).

Polypyridyl multidentate ligands based on ethylenediamine backbones are important metal-binding agents with applications in biomimetics and homogeneous catalysis. The seemingly hexadentate tpena ligand [systematic name: N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetate] reacts with zinc chloride and zinc bromide to form trichlorido[µ-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dizinc(II), [Zn2(C22H24N5O2)Cl3], and tribromido[µ-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dizinc(II), [Zn2Br3(C22H24N5O2)]. One Zn(II) ion shows the anticipated N5O coordination in an irregular six-coordinate site and is linked by an anti carboxylate bridge to a tetrahedral ZnX3 (X = Cl or Br) unit. In contrast, the Cu(II) ions in aquatribromido[µ-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dicopper(II)-tribromido[µ-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dicopper(II)-water (1/1/6.5) [Cu2Br3(C22H24N5O2)][Cu2Br3(C22H24N5O2)(H2O)]·6.5H2O, occupy two tpena-chelated sites, one a trigonal bipyramidal N3Cl2 site and the other a square-planar N2OCl site. In all three cases, electrospray ionization mass spectra were dominated by a misleading ion assignable to [M(tpena)](+) (M = Zn(2+) and Cu(2+)).