Polar Nature of (CH3NH3)3Bi2I9 Perovskite-Like Hybrids.

High-quality single crystals of perovskite-like (CH3NH3)3Bi2I9 hybrids have been synthesized, using a layered-solution crystal-growth technique. The large dielectric constant is strongly affected by the polar ordering of its constituents. Progressive dipolar ordering of the methylammonium cation upon cooling below 300 K gradually converts the hexagonal structure (space group P63/mmc) into a monoclinic phase (C2/c) at 160 K. A well-pronounced, ferrielectric phase transition at 143 K is governed by in-plane ordering of the bismuth lone pair that breaks inversion symmetry and results in a polar phase (space group P21). The dielectric constant is markedly higher in the C2/c phase above this transition. Here, the bismuth lone pair is disordered in-plane, allowing the polarizability to be substantially enhanced. Density functional theory calculations estimate a large ferroelectric polarization of 7.94 µC/cm2 along the polar axis in the P21 phase. The calculated polarization has almost equal contributions of the methylammonium and Bi3+ lone pair, which are fairly decoupled.

Towards Redox-Driven Unidirectional Molecular Motion.

Redox-driven molecular motion is an attractive alternative to light-driven processes. Here, the ability of an overcrowded alkene-based unimolecular light-driven rotary motor (A) to be driven by oxidation/reduction cycles is explored. We show that two-electron oxidation of A is followed by irreversible deprotonation and reduction to form a monocationic species D(+) , in which the stereogenic center is lost. This latter species was isolated through preparative electrolysis and its structure was confirmed by using single-crystal X-ray analysis. However, at short timescales and in the absence of Brønsted acids, these processes can be outrun and the oxidation of A to a dicationic species B(2+) occurs, in which the central double bond (the axle of the molecular motor) becomes a single bond; when followed by rapid reduction, it results in the reformation of A, potentially in both its stable and unstable conformations. The latter conformation, if formed, undergoes thermal helix inversion, completing a rotary cycle. The data obtained regarding these reactions provide a window of opportunity for the motor to be driven electrochemically, without degradation from chemical reactions of the oxidized motor.

Synthetic, crystallographic, and computational study of copper(II) complexes of ethylenediaminetetracarboxylate ligands.

Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands H(4)eda3p and H(4)eddadp (H(4)eda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; H(4)eddadp = ethylenediamine-N,N'-diacetic-N,N'-di-3-propionic acid) have been prepared. An octahedral trans(O(6)) geometry (two propionate ligands coordinated in axial positions) has been established crystallographically for the Ba[Cu(eda3p)]·8H(2)O compound, while Ba[Cu(eddadp)]·8H(2)O is proposed to adopt a trans(O(5)) geometry (two axial acetates) on the basis of density functional theory calculations and comparisons of IR and UV-vis spectral data. Experimental and computed structural data correlating similar copper(II) chelate complexes have been used to better understand the isomerism and departure from regular octahedral geometry within the series. The in-plane O-Cu-N chelate angles show the smallest deviation from the ideal octahedral value of 90°, and hence the lowest strain, for the eddadp complex with two equatorial ß-propionate rings. A linear dependence between tetragonality and the number of five-membered rings has been established. A natural bonding orbital analysis of the series of complexes is also presented.

6-[(2,4-Di-methyl-anilino)methyl-idene]-2-hy-droxy-cyclo-hexa-2,4-dienone.

In the title compound, C15H15NO2, the dihedral angle between the aromatic rings is 5.86 (6)°, and an intra-molecular N-H⋯O hydrogen bond generates an S(6) motif, which helps to stabilize the enamine-keto tautomer. An intra-molecular O-H⋯O hydrogen bond also occurs. In the crystal, inversion dimers linked by pairs of O-H⋯O hydrogen bonds generate R 2 (2)(10) loops. A C-H⋯O inter-action links the dimers into [010] chains and aromatic π-π stacking [centroid-centroid separation = 3.6131 (9) Å] also occurs.

Ligand exchange and spin state equilibria of Fe(II)(N4Py) and related complexes in aqueous media.

We report the characterization and solution chemistry of a series of Fe(II) complexes based on the pentadentate ligands N4Py (1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine), MeN4Py (1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)ethanamine), and the tetradentate ligand Bn-N3Py (N-benzyl-1,1-di(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine) ligands, i.e., [Fe(N4Py)(CH(3)CN)](ClO(4))(2) (1), [Fe(MeN4Py)(CH(3)CN)](ClO(4))(2) (2), and [Fe(Bn-N3Py)(CH(3)CN)(2)](ClO(4))(2) (3), respectively. Complexes 2 and 3 are characterized by X-ray crystallography, which indicates that they are low-spin Fe(II) complexes in the solid state. The solution properties of 1-3 are investigated using (1)H NMR, UV/vis absorption, and resonance Raman spectroscopies, cyclic voltammetry, and ESI-MS. These data confirm that in acetonitrile the complexes retain their solid-state structure, but in water immediate ligand exchange of the CH(3)CN ligand(s) for hydroxide or aqua ligands occurs with full dissociation of the polypyridyl ligand at low (<3) and high (>9) pH. pH jumping experiments confirm that over at least several minutes the ligand dissociation observed is fully reversible for complexes 1 and 2. In the pH range between 5 and 8, complexes 1 and 2 show an equilibrium between two different species. Furthermore, the aquated complexes show a spin equilibrium between low- and high-spin states with the equilibrium favoring the high-spin state for 1 but favoring the low-spin state for 2. Complex 3 forms only one species over the pH range 4-8, outside of which ligand dissociation occurs. The speciation analysis and the observation of an equilibrium between spin states in aqueous solution is proposed to be the origin of the effectiveness of complex 1 in cleaving DNA in water with (3)O(2) as terminal oxidant.

An enantioselective synthetic route toward second-generation light-driven rotary molecular motors.

Controlling the unidirectional rotary process of second-generation molecular motors demands access to these motors in their enantiomerically pure form. In this paper, we describe an enantioselective route to three new second-generation light-driven molecular motors. Their synthesis starts with the preparation of an optically active alpha-methoxy-substituted upper-half ketone involving an enzymatic resolution. The subsequent conversion of this ketone to the corresponding hydrazone by treatment with hydrazine led to full racemization. However, conversion to a TBDMS-protected hydrazone by treatment with bis-TBDMS hydrazine, prepared according to a new procedure, proceeds with nearly full retention of the stereochemical integrity. Oxidation of the TBDMS-protected hydrazone and subsequent coupling to a lower-half thioketone followed by recrystallization provided the molecular motors with >99% ee. As these are the first molecular motors that have a methoxy substituent at the stereogenic center, the photochemical and thermal isomerization steps involved in the rotary cycle of one of these new molecules were studied in detail with various spectroscopic techniques.

Ultrafast light-driven nanomotors based on an acridane stator.

A series of molecular motors featuring a symmetrical acridane stator is reported. Photochemical and thermal isomerization experiments confirm that this stator, in combination with a thiopyran rotor, results in molecular rotary motion in which the rate-determining thermal helix inversion proceeds effectively only at temperatures above 373 K. The introduction of a cyclopentanylidene rotor unit results in a decrease in steric hindrance with respect to the stator, and as a consequence, a 10(12)-fold increase in the rate of thermal helix inversion is observed. Nanosecond transient absorption spectroscopy allows for the thermal processes to be followed accurately at ambient temperature. The rotary motor is shown to be able to operate at 0.5 MHz rotational frequencies under optimal conditions.

Spectroscopic and magnetic properties of a series of µ-cyano bridged bimetallic compounds of the type M(II)-NC-Fe(III) (M = Mn, Co, and Zn) using the building block [Fe(III)(CN)5imidazole]2-.

In this contribution, we describe the preparation and single-crystal X-ray diffraction of a new building block for bimetallic solid state materials. X-ray diffraction data of these complexes indicate that (PPh(4))(2)[Fe(CN)(5)imidazole]·2H(2)O crystallizes in the triclinic space group P1 with a = 9.8108(15) Å, b = 11.1655(17) Å, c = 23.848(4) Å, α = 87.219(2)°, ß = 85.573(2)°, γ = 70.729(2)°, and Z = 2, while its precursor Na(3)[Fe(CN)(5)(en)]·5H(2)O crystallizes in the monoclinic space group P2(1)/n with a = 8.3607(7) Å, b = 11.1624(9) Å, c = 17.4233(14) Å, ß = 90.1293(9)°, and Z = 4. Spectroscopic and magnetic properties of a series of bimetallic materials were obtained by reaction of the complex [Fe(CN)(5)imidazole](2-) with hydrated transition metal ions [M(H(2)O)(n)](2+) (M = Mn, Co, Zn; n = 4 or 6). The new bimetallic materials obtained are [Co(H(2)O)(2)][Fe(CN)(5)imidazole]·2H(2)O (1), [Mn(CH(3)OH)(2)][Fe(CN)(5)imidazole] (2), Zn[Fe(CN)(5)imidazole]·H(2)O (3), and [Mn(bpy)][Fe(CN)(5)imidazole].H(2)O (4). All of the complexes crystallize in the orthorhombic system. X-ray single-crystal analysis of the compounds identified the Imma space group with a = 7.3558(10) Å, b = 14.627(2) Å, c = 14.909(2) Å, and Z = 4 for 1; the P2(1)2(1)2(1) space group with a = 7.385(5) Å, b = 13.767(9) Å, c = 14.895(10) Å, and Z = 4 for 2; the Pnma space group with a = 13.783(2) Å, b = 7.167(11) Å, c = 12.599(2) Å, and Z = 4 for 3; and the Pnma space group with a = 13.192(3) Å, b = 7.224(16) Å, c = 22.294(5) Å, and Z = 4 for 4. The structures of 1, 2, and 4 consist of two-dimensional network layers containing, as the repeating unit, a cyclic tetramer [M(2)Fe(2)(CN)(4)] (M = Mn, Co). H bonding between the layers in the structure of 1 results in a quasi-three-dimensional network. The structure of 3 was found to be three-dimensional, where all of the cyano ligands are involved in bridging between the metal centers. The bridging character of the cyano is confirmed spectroscopically. The magnetic properties have been investigated for all of the bimetallic systems. Compound 1 shows ferromagnetic behavior with an ordering temperature at 25 K, which is higher than the corresponding Prussian Blue analogue Co(x)[Fe(CN)(6)](y) ·zH(2)O. Compound 2 shows weak ferromagnetic behavior and an interlayer antiferromagnetic character, while 3, as expected, shows paramagnetic character due to the diamagnetic character of Zn(2+). Compound 4 shows antiferromagnetic behavior.

Versatile coordination of cyclopentadienyl-arene ligands and its role in titanium-catalyzed ethylene trimerization.

Cationic titanium(IV) complexes with ansa-(eta(5)-cyclopentadienyl,eta(6)-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C(1) bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the eta(6)-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(N(i)Pr(2))(NC(6)H(4)-4-Me)(+) feature eta(1)-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.

A kinetic and structural investigation of DNA-based asymmetric catalysis using first-generation ligands.

The recently developed concept of DNA-based asymmetric catalysis involves the transfer of chirality from the DNA double helix in reactions using a noncovalently bound catalyst. To date, two generations of DNA-based catalysts have been reported that differ in the design of the ligand for the metal. Herein we present a study of the first generation of DNA-based catalysts, which contain ligands comprising a metal-binding domain linked through a spacer to a 9-aminoacridine moiety. Particular emphasis has been placed on determining the effect of DNA on the structure of the Cu(II) complex and the catalyzed Diels-Alder reaction. The most important findings are that the role of DNA is limited to being a chiral scaffold; no rate acceleration was observed in the presence of DNA. Furthermore, the optimal DNA sequence for obtaining high enantioselectivities proved to contain alternating GC nucleotides. Finally, DNA has been shown to interact with the Cu(II) complex to give a chiral structure. Comparison with the second generation of DNA-based catalysts, which bear bipyridine-type ligands, revealed marked differences, which are believed to be related to the DNA microenvironment in which the catalyst resides and where the reaction takes place.

Fast racemisation of chiral amines and alcohols by using cationic half-sandwich ruthena- and iridacycle catalysts.

The lipase-catalysed resolution of alcohols and amines yields only 50 % of the desired enantiopure product. However, addition of a racemisation catalyst leads to 100 % yield in what is called a dynamic kinetic resolution (DKR). There is a need for new racemisation catalysts that are fast and compatible with the conditions of the enzymatic reaction. We show that cationic half-sandwich ruthena- and iridacycle complexes are highly active and efficient in the racemisation of chiral alcohols and amines. Upon activation with base, these complexes are able to selectively racemise alcohols, whereas the non-activated complexes are selective catalysts for the racemisation of amines. We have applied the iridacycles in the DKR of racemic beta-chloroalcohols to produce chiral epoxides in a biphasic system in good yields and high ee (ee=enantiomeric excess).

Balancing hydrogen bonding and van der Waals interactions in cyclohexane-based bisamide and bisurea organogelators.

The solvent dependence of the gelation properties, the thermotropic behavior, and the melting enthalpy of a series of enantiomerically pure cyclohexane-based bisamide and bisurea compounds are reported. The two series of gelators examined are related structurally with the intermolecular interactions responsible for gelation differing in a systematic manner through varying the length of the alkyl tail and the number of hydrogen bonding units present. The gelation properties of the compounds in decalin, DMSO, and 1-propanol were studied by FTIR spectroscopy and by comparison of the thermal stability of their gels as determined by dropping ball experiments and by differential scanning calorimetry (DSC). FTIR spectroscopy, supported by the single-crystal X-ray diffraction of a3, indicates that the gelator molecules are aggregated through intermolecular hydrogen bonding in all of the solvents examined. The thermal stability of the gels in apolar and polar solvents was found to be dependent primarily on the relative strength of intermolecular hydrogen bonding and van der Waals interactions, respectively, compared with the strength of solvent-gelator interactions. The results of DSC indicated that the contribution of the difference in intergelator van der Waals interactions, compared with the gelator-solvent van der Waals and hydrogen bonding interactions, provided by the alkyl tail to the stability of the gel has a linear relationship with the number of methylene units in alkyl chains of length greater than six. In polar solvents, this contribution lies between 3.5 and 4.2 kJ mol(-1) per methylene unit, and in apolar solvents, it is 2.2 kJ mol(-1). The hydrogen bonding interactions were weaker in polar solvents and hence gelation occurred only where sufficient compensation was provided by intergelator van der Waals interactions. The results show that the direct relation of gelation strength to changes in solvent properties is not possible and more complex relationships should be considered. Furthermore, it is apparent that the development of design rules for the construction of LMWG molecules incorporating more than one anisotropic growth element must take into consideration the role of the solvent in determining which of the contributions is dominant.

Pentaarylfullerenes as noncoordinating cyclopentadienyl anions.

The first example of an early-transition-metal complex involving a pentaarylfullerene was prepared. Instead of half-sandwich complexes, solvent separated ion pairs were obtained in which the pentaarylfullerene moiety acts as noncoordinating cyclopentadienyl anion.

[3.3]Dithia-bridged cyclophanes featuring a thienothiophene ring: synthesis, structures and conformational analysis.

The synthesis of [3.3]dithia-bridged cyclophanes 7, 9 and 11 incorporating a fused heterocycle, thieno[2,3-b]thiophene is described. The structures are established by ¹H NMR analysis and, in the case of 11, also by single crystal X-ray crystallography. Conformational analysis by variable temperature NMR suggests that cyclophanes 7, 9 and 11 exhibit conformationally rigid bridges and rings at least up to 130° C. Energy minimization of 11 revealed anti-11 to be the most stable conformation. Although, the computed energy difference between the most stable conformation anti-11 and the next higher energy conformation syn-anti-11 is only 2.98 kJ/mol, it is intriguing that 11 does not exhibit thia-bridge inversion even at elevated temperatures.

Light-controlled supramolecular helicity of a liquid crystalline phase using a helical polymer functionalized with a single chiroptical molecular switch.

Control over the preferred helical sense of a poly(n-hexyl isocyanate) (PHIC) by using a single light-driven molecular motor, covalently attached at the polymer's terminus, has been accomplished in solution via a combination of photochemical and thermal isomerizations. Here, we report that after redesigning the photochromic unit to a chiroptical molecular switch, of which the two states are thermally stable but photochemically bistable, the chiral induction to the polymer's backbone is significantly improved and the handedness of the helical polymer is addressable by irradiation with two different wavelengths of light. Moreover, we show that the chiral information is transmitted, via the macromolecular level of the polyisocyanate, to the supramolecular level of a lyotropic cholesteric liquid crystalline phase consisting of these stiff, rodlike polymers. This allows the magnitude and sign of the supramolecular helical pitch of the liquid crystal film to be fully controlled by light.

MHz unidirectional rotation of molecular rotary motors.

A combination of cryogenic UV-vis and CD spectroscopy and transient absorption spectroscopy at ambient temperature is used to study a new class of unidirectional rotary molecular motors. Stabilization of unstable intermediates is achieved below 95 K in propane solution for the structure with the fastest rotation rate, and below this temperature measurements on the rate limiting step in the rotation cycle can be performed to obtain activation parameters. The results are compared to measurements at ambient temperature using transient absorption spectroscopy, which show that behavior of these motors is similar over the full temperature range investigated, thereby allowing a maximum rotation rate of 3 MHz at room temperature under suitable irradiation conditions.

New mechanistic insight in the thermal helix inversion of second-generation molecular motors.

The introduction of dibenzocyclohepten-5-ylidene as part of a unidirectional light-driven molecular motor allows a more complete picture of the pathway of thermal helix inversion to be developed. The most stable conformation is similar to that found in related motors in that it has, overall, an anti-folded structure with the substituent at the stereogenic centre adopting an axial orientation. Photochemical cis/trans isomerisation at -40 degrees C results in the formation of an isomer in a syn-folded conformation with the methyl group in an axial orientation. This contrasts with previous studies on related molecular rotary motors. The conformation of the higher energy intermediate typically observed for this class of compound is the anti-folded conformation, in which the methyl group is in an equatorial orientation. This conformation is available through an energetically uphill upper half ring inversion of the observed photochemical product. However, this pathway competes with a second process that leads to the more stable anti-folded conformation in which the methyl group is oriented axially. It has been shown that the conformations and pathways available for second-generation molecular motors can be described by using similar overall geometries. Differences in the metastable high-energy species are attributable to the relative energy and position on the reaction coordinate of the transition states. Kinetic studies on these new molecular motors thus provide important insights into the conformational dynamics of the rotation cycle.

Light-driven rotary molecular motors on gold nanoparticles.

We report the synthesis of unidirectional light-driven rotary molecular motors based on chiral overcrowded alkenes and their immobilisation on the surface of gold nanoparticles through two anchors. Using a combination of (1)H and (13)C NMR, UV/Vis and CD spectroscopy, we show that these motors preserve their photochemical and thermal behaviour after they have been attached to gold nanoparticles. Furthermore, we describe the synthesis of (2)H- and (13)C-labelled derivatives that were used to verify the unidirectionality of the rotary cycle of these motors both in solution and while grafted to gold nanoparticles. Taken together, these data support the conclusion that these motors maintain their unidirectional rotary cycle when grafted to the surface of small (ca. 2 nm) gold nanoparticles. Thus, continuous irradiation of the system under appropriate conditions leads to unidirectional rotation of the upper half of the molecules relative to the entire nanoparticle.

Formation of enantiopure 5-substituted oxazolidinones through enzyme-catalysed kinetic resolution of epoxides.

Halohydrin dehalogenase from Agrobacterium radiobacter catalyzed the enantioselective ring opening of terminal epoxides with cyanate as a nucleophile, yielding 5-substituted oxazolidinones in high yields and with high enantiopurity (69-98% ee). This is the first example of the biocatalytic conversion of a range of epoxides to the corresponding oxazolidinones.

Photoresponsive rolling and bending of thin crystals of chiral diarylethenes.

Dithienylhexafluorocyclopentene with (R)- or (S)-N-phenylethylamide substituents formed rod-like and 0.2-1.0 microm-thick platelike crystals by sublimation; upon UV irradiation, the crystals bent concavely to the incident light and finally rolled crystals were obtained; the bent crystals were reconverted to flat crystals by visible light irradiation.