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.

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.

The influence of alkyl chains on the performance of DSCs employing iron(II) N-heterocyclic carbene sensitizers.

The photovoltaic performances of DSCs employing two new iron(II) N-heterocyclic carbene (NHC) sensitizers are presented. The presence of n-butyl side chains had a significant impact on DSC performace. The improvement in DSC performance up to 0.93-0.95% was observed for a new heteroleptic sensitizer bearing one carboxylic acid anchoring group. The photovoltaic performance was remarkably affected by sensitization time and by a presence/absence of coadsorbent on the semiconductor surface. The highest photoconversion efficiencies (PCE) were achieved for DSCs sensitized over 17.5 hours without addition of coadsorbents. However, for a shorter dipping time of 4 hours, the presence of chenodeoxycholic acid improved the PCE from 0.46% (no coadsorbents) to 0.74%, respectively. The performance of DSCs based on a new homoleptic complex bearing two n-butyl side chains and a carboxylic acid anchor on each NHC-ligand was improved from 0.05 to 0.29% via changes in dye-bath concentration and sensitization time. The changes in the dye load on the semiconductor surface depending on the sensitization conditions were confirmed using solid-state UV-Vis spectroscopy and thermogravimetric analysis. Electrochemical impedance spectroscopy was used to gain information about the processes occurring at the different interfaces in the DSCs. The impedance response was strongly affected by the immersion time of the photoanodes in the dye-bath solutions. In the case of the homoleptic iron(II) complex, a Gerischer impedance was observed after 17.5 hours immersion. Shorter dipping times resulted in a decrease in the resistance in the system. For the heteroleptic complex, values of the chemical capacitance and electron lifetime were affected by the immersion time. However, the diffusion length was independent of sensitization conditions.

Electrolyte Tuning in Iron(II)-Based Dye-Sensitized Solar Cells: Different Ionic Liquids and I2 Concentrations.

The effects of different I2 concentrations and different ionic liquids (ILs) in the electrolyte on the performances of dye-sensitized solar cells (DSCs) containing an iron(II) N-heterocyclic carbene dye and containing the I-/I3- redox shuttle have been investigated. Either no I2 was added to the electrolyte, or the initial I2 concentrations were 0.02, 0.05, 0.10, and 0.20 M. The short-circuit current density (JSC), open-circuit voltage (VOC), and the fill factor (ff) were influenced by changes in the I2 concentration for all the ILs. For 1-hexyl-3-methylimidazole iodide (HMII), low VOC and low ff values led to poor DSC performances. Electrochemical impedance spectroscopy (EIS) showed the causes to be increased electrolyte diffusion resistance and charge transfer resistance at the counter electrode. DSCs containing 1,3-dimethylimidazole iodide (DMII) and 1-ethyl-3-methylimidazole iodide (EMII) showed the highest JSC values when 0.10 M I2 was present initially. Short alkyl substituents (Me and Et) were more beneficial than longer chains. The lowest values of the transport resistance in the photoanode semiconductor were found for DMII, EMII, and 1-propyl-2,3-dimethylimidazole iodide (PDMII) when no I2 was added to the initial electrolyte, or when [I2] was less than 0.05 M. Higher [I2] led to decreases in the diffusion resistance in the electrolyte and the counter electrode resistance. The electron lifetime and diffusion length depended upon the [I2]. Overall, DMII was the most beneficial IL. A combination of DMII and 0.1 M I2 in the electrolyte produced the best performing DSCs with an average maximum photoconversion efficiency of 0.65% for a series of fully-masked cells.

Isomers of Terpyridine as Ligands in Coordination Polymers and Networks Containing Zinc(II) and Cadmium(II).

The use of divergent 4,2':6',4″- and 3,2':6',3″-terpyridine ligands as linkers and/or nodes in extended coordination assemblies has gained in popularity over the last decade. However, there is also a range of coordination polymers which feature 2,2':6',2″-terpyridine metal-binding domains. Of the remaining 45 isomers of terpyridine, few have been utilized in extended coordination arrays. Here, we provide an overview of coordination polymers and networks containing isomers of terpyridine and either zinc(II) and cadmium(II). Although the motivation for investigations of many of these systems is their luminescent behavior, we have chosen to focus mainly on structural details, and we assess to what extent assemblies are reproducible. We also consider cases where there is structural evidence for competitive product formation. A point that emerges is the lack of systematic investigations.

Single and Double-Stranded 1D-Coordination Polymers with 4'-(4-Alkyloxyphenyl)-3,2':6',3"-terpyridines and {Cu2(µ-OAc)4} or {Cu4(µ3-OH)2(µ-OAc)2(µ3-OAc)2(AcO-κO)2} Motifs.

Five coordination polymers formed from combinations of copper(II) acetate and 4'-(4-alkyloxyphenyl)-3,2':6',3''-terpyridines with methoxy (1), n-butoxy (2), n-pentyloxy (3) and n-heptyloxy (4) substituents are reported. Reaction of 1 with Cu(OAc)2∙H2O leads to the 1D-polymer [Cu2(µ-OAc)4(1)]n in which {Cu2(-OAc)4} paddle-wheel units are connected by ligands 1, or [{Cu4(µ3-OH)2(µ-OAc)2(µ3-OAc)2(AcO-κO)2(1)2}.2MeOH]n in which centrosymmetric tetranuclear clusters link pairs of ligands 1 to give a double-stranded 1D-polymer. Layering solutions of Cu(OAc)2∙H2O (in MeOH) over 2, 3 or 4 (in CHCl3) leads to the assembly of the 1D-polymers [2{Cu2(µ-OAc)4(2)}.1.25MeOH]n, [Cu2(µ-OAc)4(3)]n and [{Cu2(µ-OAc)4(4)}.0.2CHCl3]n. In all compounds, the 3,2':6',3''-tpy unit coordinates only through the outer pyridine rings, but the conformation of the 3,2':6',3''-tpy responds to changes in the length of the alkyloxy tails leading to changes in the conformation of the polymer backbone and in the packing of the chains in the crystal lattice in the chains featuring {Cu2(-OAc)4} paddle-wheel linkers.

Porphyrin Containing Polymersomes with Enhanced ROS Generation Efficiency: In Vitro Evaluation.

Porphyrins are molecules possessing unique photophysical properties making them suitable for application in photodynamic therapy. The incorporation of porphyrins into natural or synthetic nano-assemblies such as polymersomes is a strategy to improve and prolong their therapeutic capacities and to overcome their limitations as therapeutic and diagnostic agents. Here, 5,10,15,20-tetrakis(1-(6-ethoxy-6-oxohexyl)-4-pyridin-1-io)-21H,23H-porphyrin tetrabromide porphyrin is inserted into polymersomes in order to demonstrate that the encapsulation enhances its ability to generate highly reactive singlet oxygen (1 O2 ) upon irradiation in vitro. The photoactivation of the free and polymersome-encapsulated porphyrin is evaluated by electron spin resonance and cell viability assays on three different mammalian cell lines. The results indicate that by encapsulating the porphyrin, a controlled ROS delivery within the cells is achieved, at the same time avoiding side effects such as dark toxicity, non-specific porphyrin release and over time decreased activity in vitro. This work focuses on showing a not-toxic model system for modern therapeutic nanomedicine, which works under mild irradiation and dosage conditions.

The Sting's the Thing.

Bees defend themselves by stinging and injecting a venom into their victims; bee venom is a complex mixture of chemicals including the polypeptide melittin which is mainly responsible for triggering the pain of the sting.

There Is a Future for N-Heterocyclic Carbene Iron(II) Dyes in Dye-Sensitized Solar Cells: Improving Performance through Changes in the Electrolyte.

By systematic tuning of the components of the electrolyte, the performances of dye-sensitized solar cells (DSCs) with an N-heterocyclic carbene iron(II) dye have been significantly improved. The beneficial effects of an increased Li+ ion concentration in the electrolyte lead to photoconversion efficiencies (PCEs) up to 0.66% for fully masked cells (representing 11.8% relative to 100% set for N719) and an external quantum efficiency maximum (EQEmax) up to approximately 25% due to an increased short-circuit current density (JSC). A study of the effects of varying the length of the alkyl chain in 1-alkyl-3-methylimidazolium iodide ionic liquids (ILs) shows that a longer chain results in an increase in JSC with an overall efficiency up to 0.61% (10.9% relative to N719 set at 100%) on going from n-methyl to n-butyl chain, although an n-hexyl chain leads to no further gain in PCE. The results of electrochemical impedance spectroscopy (EIS) support the trends in JSC and open-circuit voltage (VOC) parameters. A change in the counterion from I- to [BF4]- for 1-propyl-3-methylimidazolium iodide ionic liquid leads to DSCs with a remarkably high JSC value for an N-heterocyclic carbene iron(II) dye of 4.90 mA cm-2, but a low VOC of 244 mV. Our investigations have shown that an increased concentration of Li+ in combination with an optimized alkyl chain length in the 1-alkyl-3-methylimidazolium iodide IL in the electrolyte leads to iron(II)-sensitized DSC performances comparable with those of containing some copper(I)-based dyes.

Electrolyte tuning in dye-sensitized solar cells with N-heterocyclic carbene (NHC) iron(II) sensitizers.

We demonstrate that the performances of dye-sensitized solar cells (DSCs) sensitized with a previously reported N-heterocyclic carbene iron(II) dye in the presence of chenodeoxycholic acid co-adsorbant, can be considerably improved by altering the composition of the electrolyte while retaining an I-/I3 - redox shuttle. Critical factors are the solvent, presence of ionic liquid, and the use of the additives 1-methylbenzimidazole (MBI) and 4-tert-butylpyridine (TBP). For the electrolyte solvent, 3-methoxypropionitrile (MPN) is preferable to acetonitrile, leading to a higher short-circuit current density (J SC) with little change in the open-circuit voltage (V OC). For electrolytes containing MPN, an ionic liquid and MBI (0.5 M), DSC performance depended on the ionic liquid with 1-ethyl-3-methylimidazolium hexafluoridophosphate (EMIMPF) > 1,2-dimethyl-3-propylimidazolium iodide (DMPII) > 1-butyl-3-methylimidazolium iodide (BMII) ≈ 1-butyl-3-methylimidazolium hexafluoridophosphate (BMIMPF). Omitting the MBI leads to a significant improvement in J SC when the ionic liquid is DMPII, BMII or BMIMPF, but with EMIMPF the removal of the MBI additive results in a dramatic decrease in V OC (542 to 42 mV). For electrolytes containing MPN and DMPII, the effects of altering the MBI concentration have also been investigated. Although the addition of TBP improves V OC, it causes significant decreases in J SC. The best performing DSCs with the NHC-iron(II) dye employ an I-/I3 --based electrolyte with MPN as solvent, DMPII ionic liquid (0.6 M) with no or 0.01 M MBI; values of J SC = 2.31 to 2.78 mA cm-2, V OC = 292 to 374 mV have been achieved giving η in the range of 0.47 to 0.57% which represents 7.8 to 9.3% relative to an N719 reference DSC set at 100%. Electrochemical impedance spectroscopy has been used to understand the role of the MBI additive in the electrolytes.

Coumarin meets fluorescein: a Förster resonance energy transfer enhanced optical ammonia gas sensor.

This study focuses on the development of an optical ammonia gas sensor, the sensing mechanism of which is based on Förster resonance energy transfer (FRET) between coumarin and fluorescein. The dyes were immobilized into an organically modified silicate matrix during polymerizing methyltriethoxysilane with trifluoropropyltrimethoxysilane on a poly(methyl methacrylate) substrate. The resulting dye-doped xerogel films were exposed to different gaseous ammonia concentrations. A logarithmic decrease of the coumarin fluorescence emission band at 442 nm was observed with increasing gaseous ammonia concentrations, which was due to enhanced FRET between coumarin and fluorescein. The coumarin/fluorescein composition was optimized in order to obtain the best ammonia sensitivity. First experiments in a flow cell gas sensor setup demonstrated a sensitive and reversible response to gaseous ammonia.

Towards catenanes using π-stacking interactions and their influence on the spin-state of a bis(2,2':6',2"terpyridine)iron(II) domain.

The ligand 6,6"bis(4-methoxyphenyl)-4'-phenyl-2,2':6',2"terpyridine (2) has been prepared and characterized; deprotection using pyridinium chloride leads to the formation of 6,6"bis(4-hydroxyphenyl)-4'-phenyl-2,2':6',2"terpyridinium chloride ([H3]Cl). Treatment of the latter with 3-(2-(2-bromoethoxy)ethoxy)prop-1-ene under basic conditions yields ligand 4 containing pendant, alkene-terminated chains. Whereas direct complexation of 4 with ruthenium(II) proved problematical, the homoleptic complexes [Fe(2)(2)][PF(6)](2) and [Ru(2)(2)][PF(6)](2) were prepared in good to moderate yields. In the solid state, both complexes exhibit multiple face-to-face π-stacking of arene and pyridine rings which influences the coordination geometry about the metal ion. Consequential weakening of the ligand field results in [Fe(2)(2)][PF(6)](2) being high-spin. Variable temperature solution (1)H NMR spectroscopic studies confirm the iron(ii) centre remains high-spin between 200 and 295 K. The paramagnetically shifted (1)H NMR spectrum exhibits signals in the range δ 109.7 to -66.5 ppm and has been fully assigned. Paramagnetic relaxation enhancement (PRE) has been used to correlate the observed proton line-widths to the distances of the protons from the metal centre and these are in good agreement with the Fe···H separations observed in the solid state. The [Fe(2)(2)](2+) ion undergoes two dynamic processes (i) rotation of the pendant phenyl rings which is fast on the NMR timescale at 200 K, and (ii) twisting and sliding of the aromatic rings of the tpy and anisyl units which interconverts the two enantiomers of [Fe(2)(2)](2+) at 295 K.

pi-Stacking and hydrogen bonding direct diastereoselectivity in one-pot syntheses of octahedral iron(II) complexes.

One-pot reactions of FeCl(2).4H(2)O and 2,2'-bipyridine-6-carbaldehyde with enantiopure chiral amines lead to octahedral [FeL(2)](2+) complexes, the diastereoselectivity of which depends on the nature of the amine; an interplay of intra-cation pi-stacking and hydrogen bonding directs the diastereoselectivity.

All-optical integrated logic operations based on chemical communication between molecular switches.

Molecular logic gates process physical or chemical "inputs" to generate "outputs" based on a set of logical operators. We report the design and operation of a chemical ensemble in solution that behaves as integrated AND, OR, and XNOR gates with optical input and output signals. The ensemble is composed of a reversible merocyanine-type photoacid and a ruthenium polypyridine complex that functions as a pH-controlled three-state luminescent switch. The light-triggered release of protons from the photoacid is used to control the state of the transition-metal complex. Therefore, the two molecular switching devices communicate with one another through the exchange of ionic signals. By means of such a double (optical-chemical-optical) signal-transduction mechanism, inputs of violet light modulate a luminescence output in the red/far-red region of the visible spectrum. Nondestructive reading is guaranteed because the green light used for excitation in the photoluminescence experiments does not affect the state of the gate. The reset is thermally driven and, thus, does not involve the addition of chemicals and accumulation of byproducts. Owing to its reversibility and stability, this molecular device can afford many cycles of digital operation.

Vectorial property dependence in bis {4'-(n-pyridyl)-2,2':6',2"-terpyridine}iron(II) and ruthenium(II) complexes with n = 2, 3 and 4.

A comparative structural and spectroscopic investigation of the complexes [M(1)2]2+, [M(2)2]2+ and [M(3)2]2+ in which M = Fe or Ru, and ligands 1, 2 and 3 are 4'-(2-pyridyl)-, 4'-(3-pyridyl)- and 4'-(4-pyridyl)-2,2':6',2"-terpyridine, respectively, is reported. The complexes [Ru(1)2]2+, [Ru(2)2]2+ and [Ru(3)2]2+ undergo mono- and bis-N-methylation. The consequences of methylation on the absorption spectra and electrochemical properties are discussed; the solid-state structure of the bis(N-methylated) derivative of [Ru(2)2][PF6]2 is presented.

Ligands and complexes with supramolecular aromatic-aromatic interactions: iron(II) and ruthenium(II) complexes of 2,2':6',2''-terpyridines with pendant naphthalene groups.

The synthesis and characterisation of five new ligands (L), each containing a terpy binding domain and bearing a pendant naphthalene group in the 4'-position are described; homoleptic complexes, [ML2][PF6]4 (M = Fe, Ru) have been studied and structural data for four complexes are reported.

Formation of a [2 + 2]-heterotetranuclear macrocycle from reaction of a platina-homoditopic ligand with iron(II).

Reaction of 4'-(2-propyn-1-oxy)-2,2':6',2''-terpyridine (HC triple bond CCH2Oterpy) with trans-[PtI2(PEt3)2] regioselectively metallates the alkyne to give trans-[Pt(C triple bond CCH2Oterpy)2(PEt3)2] which, when treated with Fe(II), gives a [2 + 2]-metallocycle.