Introducing sterically demanding substituents and π-π-interactions into [Cu(P

A series of ten N^N chelating ligands based on a 2,2'-bipyridine (bpy) metal-binding domain and featuring sterically hindering substituents in the 6- and 6,6'-positions has been synthesized and characterized. The ligands have been incorporated into a family of 15 heteroleptic complexes of type [Cu(P^P)(N^N)][PF6] where P^P is the wide bite-angle bisphosphane ligand bis(2(diphenylphosphanyl)phenyl)ether (POP) or (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (xantphos). Substituents in several of the N^N ligands ligands possess phenyl rings remotely tethered to enable intra- and intermolecular π-π-interactions in the [Cu(P^P)(N^N)]+ cations. Single crystal X-ray structures of 12 complexes are reported. The effects of the functional groups in the bpy ligand on the photophysical properties of the complexes have been studied; solid-state emission maxima range from 518 to 567 nm. Values of the solid-state photoluminescence quantum yields (PLQYs) of the [Cu(P^P)(N^N)][PF6] compounds respond to the nature of the N^N ligand. In general, we observed that the [Cu(P^P)(N^N)]+ complexes containing 6,6'-disubstituted complexes with phenyl moieties connected via a CH2CH2 or CH2CH2CH2 spacer to the bpy domain have the highest values of PLQY. The most significant compounds are [Cu(POP)((2-PhEt)2bpy)][PF6] (PLQY = 67%) and [Cu(POP)((3-PhPr)2bpy)][PF6] (PLQY = 72%) where (2-PhEt)2bpy = 6,6'-bis(2-phenylethyl)-2,2'-bipyridine and (3-PhPr)2bpy = 6,6'-bis(3-phenylpropyl)-2,2'-bipyridine. These PLQY values are among the best performing previously reported families of [Cu(P^P)(N^N)][PF6] compounds.

Nanoparticulate Perovskites for Photocatalytic Water Reduction.

SrTiO3 and BaTiO3 nanoparticles (NPs) were activated using H2O2 or aqueous HNO3, and pristine and activated NPs were functionalized with a 2,2'-bipyridine phosphonic acid anchoring ligand (1), followed by reaction with RuCl3.3H2O and bpy, RhCl3.3H2O and bpy, or RuCl3.3H2O. The surface-bound metal complex functionalized NPs were used for the photogeneration of H2 from water, and their activity was compared to related systems using TiO2 NPs. The role of pH during surface complexation was found to be important. The NPs were characterized using Fourier transform infrared (FTIR) and solid-state absorption spectroscopies, thermogravimetric analysis mass spectrometry (TGA-MS), and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), and the dihydrogen generation was analyzed using gas chromatography-mass spectrometry (GC-MS). Our findings indicate that extensively functionalized SrTiO3 or BaTiO3 NPs may perform better than TiO2 NPs for water reduction.

Back to the future: asymmetrical DπA 2,2'-bipyridine ligands for homoleptic copper(i)-based dyes in dye-sensitised solar cells.

Metal complexes used as sensitisers in dye-sensitised solar cells (DSCs) are conventionally constructed using a push-pull strategy with electron-releasing and electron-withdrawing (anchoring) ligands. In a new paradigm we have designed new DπA ligands incorporating diarylaminophenyl donor substituents and phosphonic acid anchoring groups. These new ligands function as organic dyes. For two separate classes of DπA ligands with 2,2'-bipyridine metal-binding domains, the DSCs containing the copper(i) complexes [Cu(DπA)2]+ perform better than the push-pull analogues [Cu(DD)(AA)]+. Furthermore, we have shown for the first time that the complexes [Cu(DπA)2]+ perform better than the organic DπA dye in DSCs. The synthetic studies and the device performances are rationalised with the aid of density functional theory (DFT) and time-dependent DFT (TD-DFT) studies.

A DNA-Micropatterned Surface for Propagating Biomolecular Signals by Positional on-off Assembly of Catalytic Nanocompartments.

Signal transduction is pivotal for the transfer of information between and within living cells. The composition and spatial organization of specified compartments are key to propagating soluble signals. Here, a high-throughput platform mimicking multistep signal transduction which is based on a geometrically defined array of immobilized catalytic nanocompartments (CNCs) that consist of distinct polymeric nanoassemblies encapsulating enzymes and DNA or enzymes alone is presented. The dual role of single entities or tandem CNCs in providing confined but communicating spaces for complex metabolic reactions and in protecting encapsulated compounds from denaturation is explored. To support a controlled spatial organization of CNCs, CNCs are patterned by means of DNA hybridization to a microprinted glass surface. Specifically, CNC-functionalized DNA microarrays are produced where individual reaction compartments are kept in close proximity by a distinct geometrical arrangement to promote effective communication. Besides a remarkable versatility and robustness, the most prominent feature of this platform is the reversibility of DNA-mediated CNC-anchoring which renders it reusable. Micropatterns of polymer-based nanocompartment assemblies offer an ideal scaffold for the development of the next generation responsive and communicative soft-matter analytical devices for applications in catalysis and medicine.

Multitopic 3,2':6',3''-terpyridine ligands as 4-connecting nodes in two-dimensional 4,4-networks.

The tetratopic 1,4-bis(2-phenylethoxy)-2,5-bis(3,2':6',3''-terpyridin-4'-yl)benzene (1) and 1,4-bis(3-phenylpropoxy)-2,5-bis(3,2':6',3''-terpyridin-4'-yl)benzene (2) ligands have been prepared and fully characterised. Combination of ligand 1 or 2 and [M(hfacac)2]·xH2O (M = Cu, x = 1; M = Zn, x = 2) under conditions of crystal growth by layering led to the formation of [Cu2(hfacac)4(1)] n ·3.6n(1,2-Cl2C6H4)·2nCHCl3, [Zn2(hfacac)4(1)] n ·nMeC6H5·1.8nCHCl3, [Cu2(hfacac)4(2)] n ·nMeC6H5·2nH2O, [Cu2(hfacac)4(2)] n ·2.8nC6H5Cl and [Cu2(hfacac)4(2)] n ·2n(1,2-Cl2C6H4)·0.4nCHCl3·0.5nH2O. For each compound, single-crystal X-ray analysis revealed the assembly of a planar (4,4)-net in which the tetratopic ligands 1 or 2 define the nodes. The metal centres link two different bis(3,2':6',3''-tpy) ligands via the outer pyridine rings; whereas copper(ii) has N-donors in a trans-arrangement, zinc(ii) has them in cis. This difference between the copper(ii) and zinc(ii) coordination polymers modifies the architecture of the assembly without changing the underlying (4,4)-network.

A Tail Does Not Always Make a Difference: Assembly of cds Nets from Co(NCS)2 and 1,4-bis(n-Alkyloxy)-2,5-bis(3,2':6',3″-terpyridin-4'-yl)benzene Ligands.

The consistent assembly of a (65.8) cds net is observed in reactions of cobalt(II) thiocyanate with 1,4-bis(n-alkyloxy)-2,5-bis(3,2':6',3″-terpyridin-4'-yl)benzene ligands in which the n-alkyloxy substituents are n-propyl (ligand 3), n-butyl (4), n-pentyl (5), n-hexyl (6), n-heptyl (7), and n-octyl (8). Crystals were grown by layering a methanol solution of Co(NCS)2 over a 1,2-dichlorobenzene solution of each ligand. The choice of crystallization solvents is critical in directing the assembly of the cds net. Single-crystal structures of [Co(NCS)2(3)]n.3.5nC6H4Cl2, [Co(NCS)2(4)]n.5.5nC6H4Cl2, [Co(NCS)2(5)]n.4nC6H4Cl2, [Co(NCS)2(6)]n.3.8nC6H4Cl2, [Co(NCS)2(7)]n.3.1nC6H4Cl2, and [Co(NCS)2(8)]n.1.6nC6H4Cl2.2nMeOH (C6H4Cl2 = 1,2-dichlorobenzene) are presented and compared. The n-alkyloxy chains exhibit close to extended conformations and are accommodated in cavities in the lattice without perturbation of the coordination framework.

The effects of introducing terminal alkenyl substituents into the 2,2'-bipyridine domain in [Cu(N

The N^N chelating ligands 6,6'-bis(but-3-en-1-yl)-2,2'-bipyridine (1), 6-(but-3-en-1-yl)-6'-methyl-2,2'-bipyridine (2), 6,6'-bis(pent-4-en-1-yl)-2,2'-bipyridine (3) and 6-(pent-4-en-1-yl)-6'-methyl-2,2'-bipyridine (4) have been prepared, characterized, and incorporated into the heteroleptic [Cu(N^N)(P^P)][PF6] complexes in which P^P is either POP (bis(2-(diphenylphosphanyl)phenyl)ether) or xantphos (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane). The eight coordination compounds have been fully characterized, including the single crystal structures of [Cu(1)(xantphos)][PF6], [Cu(1)(POP)][PF6]·CH2Cl2, [Cu(2)(xantphos)][PF6], [Cu(2)(POP)][PF6] and [Cu(3)(POP)][PF6]·0.5Et2O. The [Cu(N^N)(P^P)]+ cations exhibit a partially reversible or irreversible Cu+/Cu2+ oxidation at more positive potentials than the benchmark [Cu(bpy)(P^P)]+ and [Cu(Me2bpy)(P^P)]+ complexes consistent with the increase in steric hindrance of the terminal alkenyl substituents. When excited in the region of the metal-to-ligand charge transfer (MLCT) absorption, solutions of the [Cu(N^N)(P^P)][PF6] complexes are weak emitters with λmaxem in the range 565-578 nm. However, powdered samples achieve photoluminescence quantum yields in the range of 28.5 to 62.3%, with the highest PLQY found for [Cu(3)(POP)][PF6] with an excited-state lifetime, τ, of 16.1 µs. For [Cu(3)(POP)][PF6], the excited state lifetime was measured in MeTHF at 293 and 77 K, and the increase in τ from 1.77 to 59.4 µs upon cooling supports thermally activated delayed fluorescence (TADF) at ambient temperatures.

Correction: A 3-dimensional {42·84} lvt net built from a ditopic bis(3,2':6',3''-terpyridine) tecton bearing long alkyl tails.

[This corrects the article DOI: 10.1039/C4CE02347A.].

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α'-Diimine Ligands.

Invited for the cover of this issue are Davood Zare, Claude Piguet, Edwin C. Constable and co-workers at the University of Basel and the University of Geneva. The image depicts a [AgI L]+ intermediate about to catch a second α,α'-diimine ligand to form the stable [AgI L2 ]+ . Read the full text of the article at 10.1002/chem.202200912.

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α'-Diimine Ligands.

The allosteric positive cooperativity accompanying the formation of compact [CuI (α,α'-diimine)2 ]+ building blocks contributed to the historically efficient synthesis of metal-containing catenates and knotted assemblies. However, its limited magnitude can easily be overcome by the negative chelate cooperativity that controls the overall formation of related polymetallic multistranded helicates and grids. Despite the more abundant use of analogous dioxygen-resistant [AgI (α,α'-diimine)2 ]+ units in modern entangled metallo-supramolecular assemblies, a related thermodynamic justification was absent. Solid-state structural characterizations show the successive formation of [AgI (α,α'-diimine)(CH3 CN)][X] and [AgI (α,α'-diimine)2 ][X] upon the stepwise reactions of α,α'-diimine=2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives with AgX (X=BF4 - , ClO4 - , PF6 - ). In room-temperature, 5-10 mM acetonitrile solutions, these cationic complexes exist as mixtures in fast exchange on the NMR timescale. Spectrophotometric titrations using the unsubstituted bpy and phen ligands point to the statistical (=non-cooperative) binding of two successive bidentate ligands around AgI , a mechanism probably driven by the formation of hydrophobic belts, that overcomes the unfavorable decrease in the positive charge borne by the metallic cation. Surprisingly, the addition of methyl groups adjacent to the nitrogen donors (6,6' positions in dmbpy; 2,9 positions in dmphen) induces positive cooperativity for the formation of [Ag(dmbpy)2 ]+ and [Ag(dmphen)2 ]+ , a trend assigned to additional stabilizing interligand interactions. Adding rigid and polarizable phenyl side arms in [Ag(Brdmbpy)2 ]+ further reinforces the positively cooperative process, while limiting the overall decrease in metal-ligand affinity.

TADF: Enabling luminescent copper(i) coordination compounds for light-emitting electrochemical cells.

The last decade has seen a surge of interest in the emissive behaviour of copper(i) coordination compounds, both neutral compounds that may have applications in organic light-emitting doides (OLEDs) and copper-based ionic transition metal complexes (Cu-iTMCs) with potential use in light-emitting electrochemical cells (LECs). One of the most exciting features of copper(i) coordination compounds is their possibility to exhibit thermally activated delayed fluorescence (TADF) in which the energy separation of the excited singlet (S1) and excited triplet (T1) states is very small, permitting intersystem crossing (ISC) and reverse intersystem crossing (RISC) to occur at room temperature without the requirement for the large spin-orbit coupling inferred by the presence of a heavy metal such as iridium. In this review, we focus mainly in Cu-iTMCs, and illustrate how the field of luminescent compounds and those exhibiting TADF has developed. Copper(i) coordination compounds that class as Cu-iTMCs include those containing four-coordinate [Cu(P^P)(N^N)]+ (P^P = large-bite angle bisphosphane, and N^N is typically a diimine), [Cu(P)2(N^N)]+ (P = monodentate phosphane ligand), [Cu(P)(tripodal-N3)]+, [Cu(P)(N^N)(N)]+ (N = monodentate N-donor ligand), [Cu(P^P)(N^S)]+ (N^S = chelating N,S-donor ligand), [Cu(P^P)(P^S)]+ (P^S = chelating P,S-donor ligand), [Cu(P^P)(NHC)]+ (NHC = N-heterocyclic carbene) coordination domains, dinuclear complexes with P^P and N^N ligands, three-coordinate [Cu(N^N)(NHC)]+ and two-coordinate [Cu(N)(NHC)]+ complexes. We pay particular attention to solid-state structural features, e.g. π-stacking interactions and other inter-ligand interactions, which may impact on photoluminescence quantum yields. Where emissive Cu-iTMCs have been tested in LECs, we detail the device architectures, and this emphasizes differences which make it difficult to compare LEC performances from different investigations.

Attraction in Action: Reduction of Water to Dihydrogen Using Surface-Functionalized TiO2 Nanoparticles.

The reactivity of a heterogeneous rhodium(III) and ruthenium(II) complex-functionalized TiO2 nanoparticle (NP) system is reported. The ruthenium and rhodium metal complexes work in tandem on the TiO2 NPs surface to generate H2 through water reduction under simulated and normal sunlight irradiation. The functionalized TiO2 NPs outperformed previously reported homogeneous systems in turnover number (TON) and frequency (TOF). The influence of individual components within the system, such as pH, additive, and catalyst, were tested. The NP material was characterized using TGA-MS, 1H NMR spectroscopy, FTIR spectroscopy, solid absorption spectroscopy, and ICP-MS. Gas chromatography was used to determine the reaction kinetics and recyclability of the NP-supported photocatalyst.

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.

Solar energy conversion using first row d-block metal coordination compound sensitizers and redox mediators.

The use of renewable energy is essential for the future of the Earth, and solar photons are the ultimate source of energy to satisfy the ever-increasing global energy demands. Photoconversion using dye-sensitized solar cells (DSCs) is becoming an established technology to contribute to the sustainable energy market, and among state-of-the art DSCs are those which rely on ruthenium(ii) sensitizers and the triiodide/iodide (I3 -/I-) redox mediator. Ruthenium is a critical raw material, and in this review, we focus on the use of coordination complexes of the more abundant first row d-block metals, in particular copper, iron and zinc, as dyes in DSCs. A major challenge in these DSCs is an enhancement of their photoconversion efficiencies (PCEs) which currently lag significantly behind those containing ruthenium-based dyes. The redox mediator in a DSC is responsible for regenerating the ground state of the dye. Although the I3 -/I- couple has become an established redox shuttle, it has disadvantages: its redox potential limits the values of the open-circuit voltage (V OC) in the DSC and its use creates a corrosive chemical environment within the DSC which impacts upon the long-term stability of the cells. First row d-block metal coordination compounds, especially those containing cobalt, and copper, have come to the fore in the development of alternative redox mediators and we detail the progress in this field over the last decade, with particular attention to Cu2+/Cu+ redox mediators which, when coupled with appropriate dyes, have achieved V OC values in excess of 1000 mV. We also draw attention to aspects of the recyclability of DSCs.

Stars and stripes: hexatopic tris(3,2':6',3''-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers.

The hexatopic ligands 1,3,5-tris(4,2':6',4''-terpyridin-4'-yl)benzene (1), 1,3,5-tris(3,2':6',3''-terpyridin-4'-yl)benzene (2), 1,3,5-tris{4-(4,2':6',4''-terpyridin-4'-yl)phenyl}benzene (3), 1,3,5-tris{4-(3,2':6',3''-terpyridin-4'-yl)phenyl}benzene (4) and 1,3,5-trimethyl-2,4,6-tris{4-(3,2':6',3''-terpyridin-4'-yl)phenyl}benzene (5) have been prepared and characterized. The single crystal structure of 1·1.75DMF was determined; 1 exhibits a propeller-shaped geometry with each of the three 4,2':6',4''-tpy domains being crystallographically independent. Packing of molecules of 1 is dominated by face-to-face π-stacking interactions which is consistent with the low solubility of 1 in common organic solvents. Reaction of 5 with [Cu(hfacac)2]·H2O (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) under conditions of crystal growth by layering resulted in the formation of [Cu3(hfacac)6(5)] n ·2.8nC7H8·0.4nCHCl3. Single-crystal X-ray diffraction reveals an unusual 1D-coordination polymer consisting of a series of alternating single and double loops. Each of the three crystallographically independent Cu atoms is octahedrally sited with cis-arrangements two N-donors from two different ligands 1 and, therefore, cis-arrangements of coordinated [hfacac]- ligands; this observation is unusual among compounds in the Cambridge Structural Database containing {Cu(hfacac)2N2} coordination units in which the two N-donors are in a non-chelating ligand.

Expanded Ligands Based upon Iron(II) Coordination Compounds of Asymmetrical Bis(terpyridine) Domains.

The synthesis and characterization of two tritopic ligands containing a 2,2':6',2″-terpyridine (tpy) metal binding domain and either a 3,2':6',3″- or a 4,2':6',4″-tpy domain are detailed. The synthetic routes to these ligands involved the [Pd(dppf)Cl2]-catalyzed coupling of a boronic ester-functionalized 2,2':6',2″-tpy with bromo-derivatives of 3,2':6',3″-tpy or 4,2':6',4″-tpy. The 2,2':6',2″-tpy domains of the tritopic ligands preferentially bind Fe2+ in reactions with iron(II) salts leading to the formation of two homoleptic iron(II) complexes containing two peripheral 3,2':6',3″-tpy or 4,2':6',4″-tpy metal-binding sites, respectively. These iron(II) complexes are potentially tetratopic ligands and represent expanded versions of tetra(pyridin-4-yl)pyrazine.

A counterion study of a series of [Cu(P

The syntheses and characterisations of a series of heteroleptic copper(I) compounds [Cu(POP)(Mebpy)][A], [Cu(POP)(Me2bpy)][A], [Cu(xantphos)(Mebpy)][A] and [Cu(xantphos)(Me2bpy)][A] in which [A]- is [BF4]-, [PF6]-, [BPh4]- and [BArF4]- (Mebpy = 6-methyl-2,2'-bipyridine, Me2bpy = 6,6'-dimethyl-2,2'-bipyridine, POP = oxydi(2,1-phenylene)bis(diphenylphosphane), xantphos = (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane), [BArF4]- = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) are reported. Nine of the compounds have been characterised by single crystal X-ray crystallography, and the consequences of the different anions on the packing interactions in the solid state are discussed. The effects of the counterion on the photophysical properties of [Cu(POP)(N^N)][A] and [Cu(xantphos)(N^N)][A] (N^N = Mebpy and Me2bpy) have been investigated. In the solid-state emission spectra, the highest energy emission maxima are for [Cu(xantphos)(Mebpy)][BPh4] and [Cu(xantphos)(Me2bpy)][BPh4] (λemmax = 520 nm) whereas the lowest energy λemmax values occur for [Cu(POP)(Mebpy)][PF6] and [Cu(POP)(Mebpy)][BPh4] (565 nm and 563 nm, respectively). Photoluminescence quantum yields (PLQYs) are noticeably affected by the counterion; in the [Cu(xantphos)(Me2bpy)][A] series, solid-state PLQY values decrease from 62% for [PF6]-, to 44%, 35% and 27% for [BF4]-, [BPh4]- and [BArF4]-, respectively. This latter series of compounds was used as active electroluminescent materials on light-emitting electrochemical cells (LECs). The luminophores were mixed with ionic liquids (ILs) [EMIM][A] ([EMIM]+ = [1-ethyl-3-methylimidazolium]+) containing the same or different counterions than the copper(I) complex. LECs containing [Cu(xantphos)(Me2bpy)][BPh4] and [Cu(xantphos)(Me2bpy)][BArF4] failed to turn on under the LEC operating conditions, whereas those with the smaller [PF6]- or [BF4]- counterions had rapid turn-on times and exhibited maximum luminances of 173 and 137 cd m-2 and current efficiencies of 3.5 and 2.6 cd A-1, respectively, when the IL contained the same counterion as the luminophore. Mixing the counterions ([PF6]- and [BF4]-) of the active complex and the IL led to a reduction in all the figures of merit of the LECs.

Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2':6',3"-Terpyridines.

Coordination networks formed between Co(NCS)2 and 4'-substituted-[1,1'-biphenyl]-4-yl-3,2':6',3"-terpyridines in which the 4'-group is Me (1), H (2), F (3), Cl (4) or Br (5) are reported. [Co(1)2(NCS)2]n·4.5nCHCl3, [Co(2)2(NCS)2]n·4.3nCHCl3, [Co(3)2(NCS)2]n·4nCHCl3, [Co(4)2(NCS)2]n, and [Co(5)2(NCS)2]n·nCHCl3 are 2D-networks directed by 4-connecting cobalt nodes. Changes in the conformation of the 3,2':6',3"-tpy unit coupled with the different peripheral substituents lead to three structure types. In [Co(1)2(NCS)2]n·4.5nCHCl3, [Co(2)2(NCS)2]n·4.3nCHCl3, [Co(3)2(NCS)2]n·4nCHCl3, cone-like arrangements of [1,1'-biphenyl]-4-yl units pack through pyridine…arene π-stacking, whereas Cl…π interactions are dominant in the packing in [Co(4)2(NCS)2]n. The introduction of the Br substituent in ligand 5 switches off both face-to-face π-stacking and halogen…π-interactions, and the packing interactions are more subtly controlled. Assemblies with organic linkers 1-3 are structurally similar and the lattice accommodates CHCl3 molecules in distinct cavities; thermogravimetric analysis confirmed that half the solvent in [Co(3)2(NCS)2]n·4nCHCl3 can be reversibly removed.

What Goes in Must Come out: The Story of Uric Acid.

Birds and reptiles convert waste ammonia into uric acid, while mammals excrete urea, with only small amounts of uric acid ending up in urine. This column explores the varying roles of uric acid and important calcium and sodium salts, and introduces π-stacking interactions in solid-state structures.