Unusually short unsupported Au(III)⋯Au(III) aurophilic contacts in emissive lanthanide tetracyanoaurate(III) complexes.

A series of [Au(CN)4]- salts with lanthanide 2,2'-bipyridine dioxide cations features Au(III) aurophilic interactions between [Au(CN)4]- groups, with Au⋯Au distances of 3.3603(4) Šand 3.4354(4) Šthat are shorter than any previously reported. Computations predict the interactions to be weakly attractive; packing effects appear to also contribute to the close contacts. The materials are emissive: there is no Au(III)-based luminescence, but for Ln = Eu the PLQY of 29% is surprisingly high compared to related analogues.

Inducing ring distortions in unsubstituted metallophthalocyanines using axial N-heterocyclic carbenes.

A series of metallophthalocyanine (PcM) complexes with axial N-heterocyclic carbene ligands (NHC; 1,3-diisopropylimidazol-2-ylidene (DIP) and 1,3-dimethylbenzimidazol-2-ylidene (DMB)) were prepared and structurally characterized. PcCoII(DIP), PcZnII(DIP), and PcZnII(DMB) are five-coordinate complexes with mild dome-type Pc-ring distortions, while PcFeII(DIP)2 is six-coordinate and has a very large ruffle-type ring-distortion with respect to typical PcM(L)2 systems. The distortion is induced by the highly steric axial DIP ligands. The distortions were quantified and classified by their bond lengths and torsion angles, and according to the normal-coordinate structural decomposition (NSD) analysis. Upon ligation of the NHC, the insoluble PcM materials were solublized in common organic solvents, with typical UV-visible Q-band maxima observable between 658 and 677 nm; the increased solubility is rationalized in terms of the reduced solid-state aggregation of the complexes, attributable to the axial ligation.

Cadmium Dicyanoaurates and Their Reaction with Ammonia.

The synthesis and crystal structures of two anionic cadmium dicyanoaurate coordination polymers, [nBu4N]6[(Cd4Cl4)2(Au(CN)2)12][CdCl4] (TCCA) and [nBu4N]2[Cd(Au(CN)2)4], and their reaction with ammonia vapour is reported. TCCA and the isostructural [nBu4N]6[(Cd4Br4)2(Au(CN)2)12][CdBr4] form 3-D arrays with [Cd4X4]4+ (X=Cl, Br) cubane clusters linked from each octahedral Cd(II) centre by three bridging [Au(CN)2]- units. TCCA reacts with ammonia with concentrations of 1000 ppm or higher to give a product with a quantum yield of 0.88, while [nBu4N]2[Cd(Au(CN)2)4], which forms a 2-D anionic Cd[Au(CN)2]2 sheet structure with axially pendant [Au(CN)2]- units, reacts with concentrated ammonia vapour to generate Cd(NH3)2[Au(CN)2]2; this has a similar 2-D sheet structure but with axial NH3 units. Vibrational spectroscopy illustrated that the reaction of both Cd/[Au(CN)2]-based materials with ammonia proceeded by breaking Cd-NC bonds. For [nBu4N]2[Cd(Au(CN)2)4], this results in decomposition into [nBu4N][Au(CN)2] ⋅ 0.5H2O and Cd(NH3)2[Au(CN)2]2, while the reaction of ammonia with TCCA is reversible by heating the ammonia-bound sample above 110 °C. Cd[Au(CN)2]2 can be prepared by thermal removal of NH3 units from Cd(NH3)2[Au(CN)2]2.

Anisotropic Thermal Expansion of Structurally Related Lanthanide-Mercury(II) Cyanide Coordination Polymers.

Three sets of related lanthanide-mercury(II) cyanide coordination polymers were synthesized by the reaction of LnCl3·xH2O (Ln = Ce, Nd, Eu, Gd, Tb, Dy, Ho, Tm, Yb, and Lu) with Hg(CN)2 and structurally characterized. [Ce(OH2)5][Hg(CN)2Cl]3·2H2O is a 3-D material with sheet-based architecture; its thermal expansion behavior shows uniaxial negative thermal expansion (-18.3(8), 39(2), and 68.3(16) ppm K-1 along the a, b, and c axes, respectively). This anisotropic thermal behavior is postulated to be driven elastically by weak Hg···Cl interactions: large area expansion of the sheets causes negative thermal expansion in the perpendicular direction. Using lanthanides heavier than Ce yielded 2-D sheet-based compounds with the formula [Ln(OH2)x]2[Hg(CN)2]5Cl6·2H2O (Ln = Nd and Eu, x = 7; Ln = Gd, Tb, Dy, Ho, Tm, Yb, and Lu, x = 6). Although there was also evidence for elastic behavior within these materials, both showed uniaxial zero thermal expansion (Ln = Nd: 27.9(17), 22.4(10), and 0.6(12) ppm K-1 along the I, II, and III principal axes, respectively; Ln = Tb: 39.6(12), 1.1(17), and 36.1(7) ppm K-1 along the a, b, and c axes, respectively). Despite their similar structural architecture, this zero thermal expansion was found to occur in different directions─within the plane of the 2-D sheets for [Nd(OH2)7]2[Hg(CN)2]5Cl6·2H2O but in the direction perpendicular to the 2-D sheets for [Tb(OH2)6]2[Hg(CN)2]5Cl6·2H2O. Overall, this system of compounds reveals the delicate relationship between coordination polymer structure and thermal expansion.

Tuning the visible colour of octahedral manganese(III) phthalocyanines via axial ligand exchange.

A series of [PcMnL2]SbF6 complexes (Pc = phthalocyanine) was synthesized and structurally characterized by stripping the chloride from PcMnCl with AgSbF6 in o-dichlorobenzene and adding a range of donor ligands (L = THF, pyridine, p-dimethylaminopyridine (DMAP), Ph3PO, N-methylimidazole (MeIm), MeCN) to the resulting solution. Addition of or exposure to water where L = heterocyclic amines yielded µ-oxo complexes of the form [PcMnL]2O, which were structurally characterized for L = DMAP and MeIm. The [PcMnL2]SbF6 complexes have an increased solubility in organic solvents, where the axial ligands inhibit the characteristic ring π-π aggregation of PcM complexes. A variety of colours were observed (blue/green to red/purple), with Q-band absorptions (excluding the µ-oxo species) spanning from 715-761 nm and LMCT-bands from 497-574 nm. The combination of the ligand-induced absorption shifts coupled with their relative intensities in the visible region is responsible for the observed colour range and illustrates that facile ligand exchange is a useful tool in producing materials with a variety of colours from PcMnCl.

Contemporary Strategies for Immobilizing Metallophthalocyanines for Electrochemical Transformations of Carbon Dioxide.

Metallophthalocyanine (PcM) coordination complexes are well-known mediators of the electrochemical reduction of carbon dioxide (CO2). They have many properties that show promise for practical applications in the energy sector. Such properties include synthetic flexibility, a high stability, and good efficiencies for the reduction of CO2 to useful feedstocks, such as carbon monoxide (CO). One of the ongoing challenges that needs to be met is the incorporation of PcM into the heterogeneous materials that are used in a great many CO2-reduction devices. Much progress has been made in the last decade and there are now several promising approaches to incorporate PcM into a range of materials, from simple carbon-adsorbed preparations to extended polymer networks. These approaches all have important advantages and drawbacks. In addition, investigations have led to new proposals regarding CO2 reduction catalytic cycles and other operational features that are crucial to function. Here, we describe developments in the immobilization of PcM CO2 reduction catalysts in the last decade (2013 to 2023) and propose promising avenues and strategies for future research.

Resolving a Half-Century-Long Controversy between (Magneto)optical and EPR Spectra of Single-Electron-Reduced [PcFe]-, [PcFeL]-, and [PcFeX]2- Complexes: Story of a Double Flip.

The reduction of iron(II) phthalocyanine (Pc(2-)FeII) or its bisaxially coordinated complexes results in the formation of the purple/red [PcFe]-, [PcFeL]-, and [PcFeX]2- (L is neutral and X is anionic ligand) species. The X-ray structure of the [K(DME)4][PcFe] complex exhibits a square-planar [PcFe]- anion. 1H NMR spectra of the reduced species have one or two phthalocyanine broad peaks between 15 and 17 ppm. Solution magnetic moments are consistent with the presence of a single unpaired electron. A solid-state Mössbauer spectrum of [K(DME)4][PcFe] is consistent with an early report [Taube, R. Pure Appl. Chem.1974, 38, 427-438]. The solid-state EPR spectrum of the [PcFe]- anion is close to that recorded by Konarev et al. [ Dalton Trans.2012, 41, 13841-13847]. Solution EPR spectra of reduced species have axial symmetry (g⊥ ∼ 2.08-2.17 and g|| ∼ 1.95-1.96) and correlate well with spectra reported by Lever and Wilshire in 1978 [ Inorg. Chem.1978, 17, 1145-1151]. The UV-vis spectra of pentacoordinated [PcFeL]- and [PcFeX]2- anions consist of the characteristic bands around 810, 690, and 515 nm. These bands correlate well with the set of MCD pseudo A-terms and resemble transitions in the [Pc(3-)M]- and [Pc(3-)ML]- compounds. The UV-vis and MCD spectra of [PcFeL]- and [PcFeX]2- complexes are in stark contrast to the crystallographically characterized reference [Pc(2-)CoI]- anion, which is EPR silent, has a regular diamagnetic 1H NMR spectrum, and has an intense Q-band at 699 nm, which correlates well with the strong MCD A-term. The DFT and TDDFT calculations are suggestive of the iron(II) center in a (dxy)2(dxz,yz)3(dz2)1 (s = 1) electronic configuration that is antiferromagnetically coupled with the one-electron-reduced Pc(3-) ligand (i.e., [Pc(3-)FeII]-, [Pc(3-)FeIIL]-, and [Pc(3-)FeIIX]2-). The calculated EPR, Mössbauer, and UV-vis spectra of [PcFe]-, [PcFeL]-, and [PcFeX]2- complexes are in excellent agreement with the experimental data, thus resolving the controversy between axial s = 1/2 like EPR and Pc(3-)-like UV-vis spectra of these compounds.

Highly emissive polymorphs of anhydrous cadmium tetracyanoplatinate and their solvated coordination networks.

Two anhydrous polymorphs of cadmium cyanoplatinate Cd[Pt(CN)4] coordination polymers have been synthesized and thermally, spectroscopically, and structurally characterized. α-Cd[Pt(CN)4] and ß-Cd[Pt(CN)4] are densely packed, highly emissive 3-D solids, with quantum yields of 0.85 (λem = 520 nm) and 0.79 (λem = 448 nm) respectively. Their mutual hydrate, Cd(H2O)[Pt(CN)4]·2H2O, forms a complex 3-D coordination polymer with Cd-O-Cd bridges and Pt-Pt interactions. Additionally, exposure of solid α-Cd[Pt(CN)4] and ß-Cd[Pt(CN)4] to several solvent vapours results in the formation of 2-D cyanometallate sheets of the adduct compounds CdL2[Pt(CN)4] (L = DMSO, DMF, and pyridine). Cd(pyridine)2[Pt(CN)4] shows a significantly lower quantum yield (0.32) in comparison to the parent Cd[Pt(CN)4] coordination polymers. Upon heating CdL2[Pt(CN)4] preferentially forms the kinetic product α-Cd[Pt(CN)4].

Exciton Coupling in Redox-Active Salen based Self-Assembled Metallacycles.

The incorporation of a redox-active nickel salen complex into supramolecular structures was explored via coordination-driven self-assembly with homobimetallic ruthenium complexes (bridged by oxalato or 5,8-dihydroxy-1,4-naphthoquinato ligands). The self-assembly resulted in the formation of a discrete rectangle using the oxalato complex and either a rectangle or a catenane employing the larger naphthoquinonato complex. The formation of the interlocked self-assembly was determined to be solvent and concentration dependent. The electronic structure and stability of the oxidized metallacycles was probed using electrochemical experiments, UV-Vis-NIR absorption, EPR spectroscopy and DFT calculations, confirming ligand radical formation. Exciton coupling of the intense near-infrared (NIR) ligand radical intervalence charge transfer (IVCT) bands provided further confirmation of the geometric and electronic structures in solution.

Synthesis and Structural Characterization of a Silver(I) Pyrazolato Coordination Polymer.

Coinage metal(I)···metal(I) interactions are widely of interest in fields such as supramolecular assembly and unique luminescent properties, etc. Only two types of polynuclear silver(I) pyrazolato complexes have been reported, however, and no detailed spectroscopic characterizations have been reported. An unexpected synthetic method yielded a polynuclear silver(I) complex [Ag(µ-L1Clpz)]n (L1Clpz- = 4-chloride-3,5-diisopropyl-1-pyrazolate anion) by the reaction of {[Ag(µ-L1Clpz)]3}2 with (nBu4N)[Ag(CN)2]. The obtained structure was compared with the known hexanuclear silver(I) complex {[Ag(µ-L1Clpz)]3}2. The Ag···Ag distances in [Ag(µ-L1Clpz)]n are slightly shorter than twice Bondi's van der Waals radius, indicating some Ag···Ag argentophilic interactions. Two Ag-N distances in [Ag(µ-L1Clpz)]n were found: 2.0760(13) and 2.0716(13) Å, and their N-Ag-N bond angles of 180.00(7)° and 179.83(5)° indicate that each silver(I) ion is coordinated by two pyrazolyl nitrogen atoms with an almost linear coordination. Every five pyrazoles point in the same direction to form a 1-D zig-zag structure. Some spectroscopic properties of [Ag(µ-L1Clpz)]n in the solid-state are different from those of {[Ag(µ-L1Clpz)]3}2 (especially in the absorption and emission spectra), presumably attributable to this zig-zag structure having longer but differently arranged intramolecular Ag···Ag interactions of 3.39171(17) Å. This result clearly demonstrates the different physicochemical properties in the solid-state between 1-D coordination polymer and metalacyclic trinuclear (hexanuclear) or tetranuclear silver(I) pyrazolate complexes.

Structural Diversity of F-Element Monophthalocyanine Complexes.

The preparation and structural characterization of a series of lanthanide and uranium(IV) phthalocyanine halide complexes were achieved by reaction of the corresponding metal halide with Li2 Pc. A preliminary survey of their reactivity includes ring reduction of Li(THF)4 [PcUCl3 ] with KC8 leading to the first structurally characterized Pc4- actinide complex, hydrolysis of PcDyCl(DMSO) to PcDyOH(H2 O)3 and preparation of a unique trimeric triangular Li(PcDy)3 (OH)4 (H2 O) cluster.

Synthesis of Sterically Congested 2,2'-Bi(Adamantyl)-Based Alcohol and Amines.

Sterically congested chiral alcohol and amines have gained tremendous attention in the design of asymmetric catalysts. Herein, the synthesis of a sterically congested bis-adamantane framework-based chiral alcohol, (1R,2S,3S,4R)-4-(2-adamantyl)adamantan-2-ol, and amine, (1R,2S,3S,4R)-4-(2-adamantyl)adamantan-2-amine, is described. Access to these sterically encumbered compounds is found via the preparation of an enantioenriched 4-adamantyladamantan-2-one intermediate, which was synthesized in 6 steps from adamantan-2-one. The key step involved enzyme-catalyzed ester hydrolysis in giving unsaturated alcohol with an enantiomeric excess of >95%. This adamantylidene adamantanol was subjected to an acid-catalyzed intramolecular [1,4] shift to give the key chiral intermediate without racemization. This ketone intermediate was transformed into the target compounds via reduction and reductive amination protocols.

Zinc Tetracyanoplatinate: A Reversible Luminescence-Based Ammonia Sensor.

ZnPt(CN)4 was shown to be an effective material for ammonia sensing, and can be synthesized using either solution or mechanochemical methods. A combination of luminescence and Raman spectroscopy revealed that multiple species are involved in the reaction between ammonia and ZnPt(CN)4 . The crystal structure of one of these species, Zn(NH3 )2 Zn(NH3 )3 (Pt(CN)4 )2 , was elucidated. Detection of ammonia vapor down to 50 ppm in air was accomplished by monitoring the luminescence spectrum. The reaction between ZnPt(CN)4 and ammonia vapor is reversible, and can be cycled multiple times by either flowing air over the material or heating. ZnPt(CN)4 also has a relatively high thermal stability, decomposing only when heated above 420 °C.

Facile tuning of strong near-IR absorption wavelengths in manganese(iii) phthalocyanines via axial ligand exchange.

The facile tuning of near-infrared absorption of manganese(iii) phthalocyanines was accomplished by changing the nature and number of bound axial ligands. For a series of axial ligands on manganese α-octabutoxyphthalocyanine and α-octakis-(isopropylthio)phthalocyanine, the electron density on the metal and its displacement from the Pc-ring plane both control the position of the complex's Q-band. For these two macrocycles, this strong absorption band could be tuned over a λmax range of 815-948 nm by axial ligand exchange.

Coordination-driven assembly of a supramolecular square and oxidation to a tetra-ligand radical species.

The design and synthesis of a supramolecular square was achieved by coordination-driven assembly of redox-active nickel(ii) salen linkers and (ethylenediamine)palladium(ii) nodes. The tetrameric geometry of the supramolecular structure was confirmed via MS, NMR, and electrochemical experiments. While oxidation of the monomeric metalloligand Schiff-base affords a Ni(iii) species, oxidation of the coordination-driven assembly results in ligand radical formation.

Ring-Oxidized Zinc(II) Phthalocyanine Cations: Structure, Spectroscopy, and Decomposition Behavior.

A bromonium oxidizing agent was used to produce a ring-oxidized zinc phthalocyanine (PcZn), [PcZn(solvent)]•2[BArF4]2 (1·solvent), in good yield. This material is dimeric in the solid state with one axially coordinated solvent [tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME)] and close intradimer ring-ring distances of 3.18 and 3.136 Å (THF and DME respectively); this proximity facilitates strong antiferromagnetic coupling to yield diamagnetic dimers. 1·THF is present in solution as a monomer and a dimer. In CH2Cl2, the dimer is favored above 0.1 mM, and it is almost exclusively present in solvents with a high dielectric constant such as acetonitrile. The material 1·THF/DME decomposes in DME to a meso-nitrogen-protonated species, [HPcZn(DME)2][BArF4] (2), which was isolated and represents the first example of such a structurally characterized, protonated, unsubstituted PcM complex. A partially oxidized dimer or "pimer" [(PcZn(DME))2]•[BArF4] (3) was also structurally characterized and has a intradimer ring-ring distance of 3.192 Å, similar to 1·THF/DME. Dimer 3 also represents the first isolated PcM-based pimer. Electron paramagnetic resonance analysis of a 1.0 mM solution of 1·DME in DME showed the production of 3 over hours by the combination of 1·DME and 2 in solution.

Redox behaviour of ([fc(NPiPr2)2]Fe)2, formation of an iron-iron bond and cleavage of azobenzene.

The redox behaviour of the dimeric tetrairon complex, ([fc(NPiPr2)2]Fe)2 (where fc(NPiPr2)2 = 1,1'-(C5H4NPiPr2)2Fe) has been investigated. Upon reduction with KC8 an Fe-Fe bond is formed with the complex maintaining a high spin configuration and having the formula [K(THF)6]([fc(NPiPr2)2]Fe)2. In contrast, oxidation of the complex is ligand based; for example, addition of the 1,2-diiodoethane (I2 equivalent) results in the formation of the monomeric iron(ii) diiodide [fc(NiPr2I)2]FeI2 wherein the phosphine is oxidized. The dimeric tetrairon complex reacts photolytically with azobenzene, cleaving the N[double bond, length as m-dash]N double bond and forming the new monomeric bis(phosphoramidate) iron complex. [fc(NP(NPh)iPr2)2]Fe. Characterization of these paramagnetic complexes was accomplished by magnetic susceptibility studies and X-ray analyses.

Phthalocyanine as a redox-active platform for organometallic chemistry.

A systematic approach to the synthesis of σ-organometallophthalocyanines is described. Structurally characterized σ-organoPcM complexes are presented, including the first PcCr-aryl, PcCr-alkynyl, and PcCr-Wittig complexes - representing the first examples of these classes of complexes for any metallophthalocyanine - and the first PcCr-alkyl complexes, which span three chromium and two Pc-ring oxidation states. This represents a rational marriage of the broad organometallic and phthalocyanine fields, opening the door for the exploration of this classical, stable, redox-active macrocycle as an ancillary ligand in metal-carbon chemistry.

Designing anisotropic cyanometallate coordination polymers with unidirectional thermal expansion (TE): 2D zero and 1D colossal positive TE.

Oxidative addition of halogens to tetracyanoplatinate results in the formation of a Pt(iv)-building block that, combined with Cu(ii), forms coordination polymers Cu(H2O)2[PtX2(CN)4] (X = Br, Cl). These materials exhibit directional anisotropic thermal expansion: nearly zero expansion within the cyanometallate sheets and positive thermal expansion in the third dimension.

Copper(II) Dihalotetracyanoplatinate(IV) Coordination Polymers and Their Vapochromic Behavior.

The coordination polymers [Cu(H2O)2(µ2-NC)4PtX2] (X = Cl, Br) form networks of square grid sheets that align in a staggered manner with one another via weak X···X interactions. Upon stepwise dehydration, the layers fuse, forming a 3-D network of distorted cubes. The materials were tested for visible vapochromic, Raman, and IR response to dimethyl sulfoxide, N,N-dimethylformamide, and pyridine. Analyte-bound coordination polymers of the form Cu(analyte)2[PtX2(CN)4] were structurally characterized by PXRD and found to form layers of square grids that align through X···X interactions. The reaction of [Cu(H2O)2(µ2-NC)4PtX2] with concentrated aqueous NH3 generated [PtBr(CN)4(NH3)]- and [PtCl(CN)4(OH)]2- anions that were incorporated into 1-D chain structures. UV-visible reflectance data show that a combination of shifting d-d transitions and the visible Br-Pt LMCT absorption band in [Cu(H2O)2(µ2-NC)4PtBr2] results in a greater vapochromic effect in comparison to that in chlorine-containing analogues.