Photo- and Stress-Induced Bending of (E)-1,2-Bis(pyridinium-4-yl)ethene Dinitrate Crystals.

We report on the elastic and photodynamic properties of (E)-1,2-bis(pyridinium-4-yl)ethene dinitrate [H2Ebpe](NO3)2, whose needle-like crystals can be reversibly deformed by applying external mechanical stress. The macro-scale mechanical properties of [H2Ebpe](NO3)2 crystals were quantified by a three-point bending test, which gave a stress-strain curve with an elastic modulus of 1.18 GPa, and its values are lower than those of other flexible elastic organic crystals. It can also be reversibly bent through the [2+2] cycloaddition reaction of the olefin moiety, depending on the direction of UV irradiation.

Woven, Polycatenated, or Cage Structures: Effect of Modulation of Ligand Curvature in Heteroleptic Uranyl Ion Complexes.

Combining the flexible zwitterionic dicarboxylate 4,4'-bis(2-carboxylatoethyl)-4,4'-bipyridinium (L) and the anionic dicarboxylate ligands isophthalate (ipht2-) and 1,2-, 1,3-, or 1,4-phenylenediacetate (1,2-, 1,3-, and 1,4-pda2-), of varying shape and curvature, has allowed isolation of five uranyl ion complexes by synthesis under solvo-hydrothermal conditions. [(UO2)2(L)(ipht)2] (1) and [(UO2)2(L)(1,2-pda)2]·2H2O (2) have the same stoichiometry, and both crystallize as monoperiodic coordination polymers containing two uranyl-(anionic carboxylate) strands united by L linkers into a wide ribbon, all ligands being in the divergent conformation. Complex 3, [(UO2)2(L)(1,3-pda)2]·0.5CH3CN, with the same stoichiometry but ligands in a convergent conformation, is a discrete, binuclear species which is the first example of a heteroleptic uranyl carboxylate coordination cage. With all ligands in a divergent conformation, [(UO2)2(L)(1,4-pda)(1,4-pdaH)2] (4) crystallizes as a sinuous and thread-like monoperiodic polymer; two families of chains run along different directions and are woven into diperiodic layers. Modification of the synthetic conditions leads to [(UO2)4(LH)2(1,4-pda)5]·H2O·2CH3CN (5), a monoperiodic polymer based on tetranuclear (UO2)4(1,4-pda)4 rings; intrachain hydrogen bonding of the terminal LH+ ligands results in diperiodic network formation through parallel polycatenation involving the tetranuclear rings and the LH+ rods. Complexes 1-3 and 5 are emissive, with complex 2 having the highest photoluminescence quantum yield (19%), and their spectra show the maxima positions usual for tris-κ2O,O'-chelated uranyl cations.

Flexible Aliphatic Diammonioacetates as Zwitterionic Ligands in UO22+ Complexes: Diverse Topologies and Interpenetrated Structures.

N,N,N',N'-Tetramethylethane-1,2-diammonioacetate (L1) and N,N,N',N'-tetramethylpropane-1,3-diammonioacetate (L2) are two flexible zwitterionic dicarboxylates which have been used as ligands for the uranyl ion, 12 complexes having been obtained from their coupling to diverse anions, mostly anionic polycarboxylates, or oxo, hydroxo and chlorido donors. The protonated zwitterion is a simple counterion in [H2L1][UO2(2,6-pydc)2] (1), where 2,6-pydc2- is 2,6-pyridinedicarboxylate, but it is deprotonated and coordinated in all the other complexes. [(UO2)2(L2)(2,4-pydcH)4] (2), where 2,4-pydc2- is 2,4-pyridinedicarboxylate, is a discrete, binuclear complex due to the terminal nature of the partially deprotonated anionic ligands. [(UO2)2(L1)(ipht)2]·4H2O (3) and [(UO2)2(L1)(pda)2] (4), where ipht2- and pda2- are isophthalate and 1,4-phenylenediacetate, are monoperiodic coordination polymers in which central L1 bridges connect two lateral strands. Oxalate anions (ox2-) generated in situ give [(UO2)2(L1)(ox)2] (5) a diperiodic network with the hcb topology. [(UO2)2(L2)(ipht)2]·H2O (6) differs from 3 in being a diperiodic network with the V2O5 topological type. [(UO2)2(L1)(2,5-pydc)2]·4H2O (7), where 2,5-pydc2- is 2,5-pyridinedicarboxylate, is a hcb network with a square-wave profile, while [(UO2)2(L1)(dnhpa)2] (8), where dnhpa2- is 3,5-dinitro-2-hydroxyphenoxyacetate, formed in situ from 1,2-phenylenedioxydiacetic acid, has the same topology but a strongly corrugated shape leading to interdigitation of layers. (2R,3R,4S,5S)-Tetrahydrofurantetracarboxylic acid (thftcH4) is only partially deprotonated in [(UO2)3(L1)(thftcH)2(H2O)] (9), which crystallizes as a diperiodic polymer with the fes topology. [(UO2)2Cl2(L1)3][(UO2Cl3)2(L1)] (10) is an ionic compound in which discrete, binuclear anions cross the cells of the cationic hcb network. 2,5-Thiophenediacetate (tdc2-) is peculiar in promoting self-sorting of the ligands in the ionic complex [(UO2)5(L1)7(tdc)(H2O)][(UO2)2(tdc)3]4·CH3CN·12H2O (11), which is the first example of heterointerpenetration in uranyl chemistry, involving a triperiodic, cationic framework and diperiodic, anionic hcb networks. Finally, [(UO2)7(O)3(OH)4.3Cl2.7(L2)2]Cl·7H2O (12) crystallizes as a 2-fold interpenetrated, triperiodic framework in which chlorouranate undulating monoperiodic subunits are bridged by the L2 ligands. Complexes 1, 2, 3, and 7 are emissive with photoluminescence quantum yields in the range of 8-24%, and their solid-state emission spectra show the usual dependence on number and nature of donor atoms.

Cooperative Spin-State Switching and Vapochromism of Mononuclear Ni(II) Complexes by Pyridine Coordination/Decoordination.

Two mononuclear Ni(II) complexes (1 and 2) have been found to display color changes upon coordination/decoordination of pyridine, resulting in their structural transformation between square-planar and octahedral geometries as well as a change in their spin state. Compound 1 changes between red (1r) and yellow (1y) upon exposure to or elimination of pyridine, while 2 undergoes a two-step transformation, changing orange 2o (S = 0) ⇄ gray 2g' (S = 1) → yellow 2y' (S = 1) depending on the reaction time. The first step (2o → 2g') takes less than 45 min, which is significantly faster than the previously reported reaction time of 1 day for a Ni(II) complex/pyridine vapor system. Compound 2o reacting with pyridine can be easily prepared by dispersing 2g in methanol instead of annealing at high temperatures (130 °C), which can be applied to develop chemical sensors for pyridine utilizing color changes and/or magnetic switching.

Zwitterionic and Anionic Polycarboxylates as Coligands in Uranyl Ion Complexes, and Their Influence on Periodicity and Topology.

The three zwitterionic di- and tricarboxylate ligands 1,1'-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-4-carboxylate) (pL1), 1,1'-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-3-carboxylate) (mL1), and 1,1',1″-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(pyridin-1-ium-4-carboxylate) (L2) have been used as ligands to synthesize a series of 15 uranyl ion complexes involving various anionic coligands, in most cases polycarboxylates. [(UO2)2(pL1)2(cbtc)(H2O)2]·10H2O (1, cbtc4- = cis,trans,cis-1,2,3,4-cyclobutanetetracarboxylate) is a discrete, dinuclear ring-shaped complex with a central cbtc4- pillar. While [UO2(pL1)(NO3)2] (2), [UO2(pL1)(OAc)2] (3), and [UO2(pL1)(HCOO)2] (4) are simple chains, [(UO2)2(mL1)(1,3-pda)2] (5, 1,3-pda2- = 1,3-phenylenediacetate) is a daisy chain and [UO2(pL1)(pdda)]3·10H2O (6, pdda2- = 1,2-phenylenedioxydiacetate) is a double-stranded, ribbon-like chain. Both [UO2(pL1)(pht)]·5H2O (7, pht2- = phthalate) and [(UO2)3(mL1)(pht)2(OH)2] (8) crystallize as diperiodic networks with the sql topology, the latter involving hydroxo-bridged trinuclear nodes. [(UO2)2(pL1)(c/t-1,3-chdc)2] (9, c/t-1,3-chdc2- = cis/trans-1,3-cyclohexanedicarboxylate) and [UO2(pL1)(t-1,4-chdc)]·1.5H2O (10, t-1,4-chdc2- = trans-1,4-cyclohexanedicarboxylate) are also diperiodic, with the V2O5 and sql topologies, respectively. Both [(UO2)2(mL1)(c/t-1,4-chdc)2] (11) and [(UO2)2(pL1)(1,2-pda)2] (12, 1,2-pda2- = 1,2-phenylenediacetate) crystallize as diperiodic networks with hcb topology, and they display threefold parallel interpenetration. [HL2][(UO2)3(L2)(adc)3]Br (13, adc2- = 1,3-adamantanedicarboxylate) contains a very corrugated hcb network with two different kinds of cells, and the uncoordinated HL2+ molecule associates with the coordinated L2 to form a capsule containing the bromide anion. [(UO2)2(pL1)(kpim)2] (14, kpim2- = 4-ketopimelate) is a three-periodic framework with pL1 molecules pillaring fes diperiodic subunits, whereas [(UO2)2(L2)2(t-1,4-chdc)](NO3)1.7Br0.3·6H2O (15), the only cationic complex in the series, is a triperiodic framework with dmc topology and t-1,4-chdc2- anions pillaring fes diperiodic subunits. Solid-state emission spectra and photoluminescence quantum yields are reported for all complexes.

Elastic Crystalline Fibers Composed of a Nickel(II) Complex.

The generation of elastic crystalline fibers from a nonfibrous crystal of metal complex is demonstrated. Applying mechanical stimuli to a platelike crystal of NiII(salophen) [1; H2salophen = N,N'-bis(salicylidene)-o-phenylenediamine] resulted in this complex being transformed into crystal fibers, which could be bent into a loop and demonstrated its high elasticity. Single-crystal X-ray diffraction analyses revealed that the transformation reflects the presence of molecular strands that are composed of a one-dimensional assembly of the slip-stacked arrangement by nearly planar Ni(salophen) molecules. The fiber flexibility was demonstrated to be lost upon the introduction of chloroform solvent molecules into the crystal lattice by recrystallization.

Thermosalient effect of a naphthalene diimide and tetrachlorocobaltate hybrid and changes of color and magnetic properties by ammonia vapor.

An organic-inorganic hybrid metal halide (OIMH), namely the electron-deficient naphthalene diimide (NDI) and [CoCl4]2- hybrid (1), showed potential as a sensor for ammonia and amines, in addition to magnetic changes upon vapochromism. Crystal 1 exhibited thermosalient behavior such as leaping and movement, at around 130 °C, which could be explained to be associated with the removal of water molecules from the crystal lattice as shown by TGA and DSC. Compound 1 changed from green to black within 5 minutes when exposed to ammonia vapor, which was attributed to the radical formation in the NDI moiety as evidenced by ESR, and this phenomenon was preserved even when other mono- and di-alkylamines were applied. The exposure of 1 to ammonia resulted in a subsequent color alteration, progressing from black to a gradually dark orange after one day (1_NH3_1 day). This transformation was concomitant with the formation of [Co(NH3)6]3+ from [CoCl4]2-, leading to a modification of the magnetic properties from paramagnetic Co(II) (S = 3/2) to diamagnetic Co(III) (S = 0). Based on these findings, compound 1 represents the first example of an OIMH that exhibits thermosalient behaviour, color change, and magnetic conversion upon exposure to ammonia.

Nanotubule inclusion in the channels formed by a six-fold interpenetrated, triperiodic framework.

When reacted together with uranyl ions under solvo-hydrothermal conditions, a bis(pyridiniumcarboxylate) zwitterion (L) and tricarballylic acid (H3tca) give the complex [NH4]2[UO2(L)2][UO2(tca)]4·2H2O (1). The two ligands are segregated into different units, an anionic nanotubule for tca3- and a six-fold interpenetrated cationic framework with lvt topology for L. The entangled framework defines large channels which contain the square-profile nanotubules. Complex 1 has a photoluminescence quantum yield of 19% and its emission spectrum shows the superposition of the signals due to the two independent species.

Synthesis, crystal structure, and properties of methyl-substituted coronene amide analogue.

A coronene amide analogue was synthesized in six steps using an improved method at the final biarylation step. The key to the progress of palladium-mediated biarylation involved the introduction of three methyl groups to suppress the undesired reaction and the use of tri-tert-butylphosphine as the ligand for palladium. Single-crystal X-ray analysis revealed that the core unit of the coronene analogue has a non-planar structure.

Recrystallization solvent-dependent elastic/plastic flexibility of an n-dodecyl-substituted tetrachlorophthalimide.

A long alkyl-chained organic molecule, 4,5,6,7-tetrachloro-2-dodecylisoindoline-1,3-dione (1), was crystallized into needle-like crystals in dichloromethane (1DCM) or plate-like ones in tetrahydrofuran (1THF) depending on the recrystallisation solvent. X-ray crystallography analyses revealed the alkyl chains of the molecules, in which they were assembled differently, with the former responding flexibly bendable and elastic deformation, and the later being a permanent plastic one by external mechanical stress. The elastic modulus (E) and hardness (H) indicating both compliant and soft nature, reflecting their weak interaction in crystals, were quantified from the nano-indentation test.

1D Mn(III) coordination polymers exhibiting chiral symmetry breaking and weak ferromagnetism.

Mn(iii) complexes with achiral ligands, (E)-N-(2-((2-aminobenzylidene)amino)-2-methylpropyl)-5-X-2-hydroxybenzamide (HLX, X = H, Cl, Br, and I), crystallise as chiral conglomerates containing amide oxygen-bridged one-dimensional coordination polymers that exhibit weak ferromagnetism. The bulk products exhibit symmetry breaking in that they do not contain equal amounts of enantiomers, though which is the dominant species depends on the substituent X.

Solvent-Dependent Bending Ability of Salen-Derived Organic Crystals.

The formation of plastic or brittle organic crystals of salen derivatives that depend on the solvents employed for crystallization is demonstrated. Large yellow crystals (ranging from mm to cm size) of ten different salen derivatives were obtained and investigated. Among them, (bis(2-hydroxyacetophenone)ethylenediimine) 2, which was recrystallized from dichloromethane, tetrahydrofuran or chloroform, exhibited plastic deformation behaviour when mechanical force was applied to the (001) face. In contrast, when 2 was recrystallized from benzene, brittle crystals were obtained. Face indexing confirmed that different crystal faces were obtained by depending on the solvent employed for recrystallization, which leads to either flexible (plastic) or brittle crystals. Photoluminescence with a band maximum at 510 nm and thermochromism related to tautomerism between OH and NH forms were also investigated, and indicate that 2 is a flexible organic single-crystal material with multifunctional properties.

Weak ferromagnetism derived from spin canting in an amido-bridged homochiral Mn(iii) 1-D coordination polymer.

A homochiral one-dimensional (1D) Mn(iii) coordination polymer [MnL]n (1) was synthesised employing the N3O-donor tetradentate ligand (L = 2-hydroxy-N-[2-[[(2-aminophenyl)methylene]amino]-2-methylpropyl]-benzamide). The X-ray structure of 1 and its magnetic properties were investigated in detail. The crystal structure of 1 shows a homochiral helical arrangement in which spontaneous resolution has occurred, despite the ligand being achiral. Magnetic characterization revealed an antiferromagnetic interaction between manganese(iii) ions (J = -2.48 cm-1, g = 1.96) that leads to an antiferromagnetic spin-ordering phase transition at TN≈ 7 K. Noteworthily, 1 exhibits weak ferromagnetism with a relatively large coercive field of 3.0 kOe based on the spin canting, indicating the formation of a homochiral weak ferromagnet.

Wheel-type heterometallic ferromagnetic clusters: [Ni7-xMx(HL)6(µ3-OMe)4(µ3-OH)2]Cl2 (M = Zn, Co, Mn; x = 1, 3).

Wheel-type heptanuclear heterometallic clusters of stoichiometry [Ni7-xMx(HL)6(µ3-OMe)4(µ3-OH)2]Cl2 (L = 1-(2-hydroxy-3-methoxybenzamido)-2-(benzylideneamino)ethane; M = Zn2+, Co2+, Mn2+; x = 1, 3) were synthesized, and their metal ion dependent ferromagnetic properties were investigated. It was demonstrated that the central position of each cluster was occupied by a Ni2+ ion while other metal ions (Zn2+, Co2+ or Mn2+) were accommodated in peripheral positions. The magnetic interactions, anisotropy and magnetization of the resultant clusters were all influenced by the combinations of metal ions present.

Creating capsules with cubanes.

A sextuply linked capsule incorporating two Ni(ii) cubane units is formed when Ni(ii) salts are reacted with N-aminoalkyl salicylamidato ligands in a 4 : 3 ratio in methanol. With a short (propyl) alkyl substituent, additional chloride counter ions are included in the cavity by occupation of one apex of each of the linked cubanes, while with a longer (pentyl) substituent, perchlorate and tetrafluoroborate anions are included, probably by H-bonding involving hydroxyl groups on the inner apices of the cubanes, indicating that the cavity can be regarded as suited to binding of hydrophilic units despite the lipophilic character of its links. The dicubane capsules show ferromagnetic behaviour typical of Ni(ii) cubanes in general, with coupling constants dependent upon the nature of the salt-derived counter anions.