Designing supramolecular liquid-crystalline hybrids from pyrenyl-containing dendrimers and arene ruthenium metallacycles

YesThe association of the arene ruthenium metallacycle [Ru4(p-cymene)4(bpe)2(donq)2][DOS]4 (bpe = 1,2-bis(4-pyridyl)ethylene, donq = 5,8-dioxydo-1,4-naphtoquinonato, DOS = dodecyl sulfate) with pyrenyl-functionalized poly(arylester) dendrimers bearing cyanobiphenyl end-groups is reported. The supramolecular dendritic systems display mesomorphic properties as revealed by polarized optical microscopy, differential scanning calorimetry and small-angle X-ray scattering measurements. The multicomponent nature of the dendrimers and of the corresponding host–guest supramolecules (i.e., end-group mesogens, dendritic core, pyrene unit, aliphatic spacers, and metallacycle) leads to the formation of highly segregated mesophases with a complex multilayered structure due to the tendency of the various constitutive building-blocks to separate in different organized zones. The pyrenyl dendrimers exhibit a multilayered smectic A-like phase, thereafter referred to as LamSmA phase to emphasize this unaccustomed morphology. As for the corresponding Ru4–metallacycle adducts, they self-organize into a multicontinuous thermotropic cubic phase with the Im3̅m space group symmetry. This represents a unique example of liquid-crystalline behavior observed for such large and complex supramolecular host–guest assemblies. Models of their supramolecular organizations within both mesophases are proposed.R.D. thanks the Swiss National Science Foundation (Grant No 200020-140298) for financial support

High One-Dimensional Charge Mobility in Semiconducting Columnar Mesophases of Isocyano-Triphenylene Metal Complexes

Producción CientíficaThis paper reports the synthesis, liquid crystal behavior, and charge-transport properties in the mesophase of isocyano-triphenylene gold, copper, palladium, and platinum complexes [MX(CNR)] (CNR = 2-(6-(4-isocyanophenoxy)hexyloxy)-3,6,7,10,11-pentakisdodecyloxytriphenylene; M = Au, X = Cl, C6F5, C6F4OC10H21, CN; M = Cu, X = Cl), [(μ-4,4′-C6F4C6F4){Au(CNR)}2], [(μ-Cl2){Cu(CNR)2}2], and [MX2(CNR)2] (M = Pd, Pt; X = Cl, Br, I, and M = Pt, X = CN). The thermal and electronic properties of these materials are modulated by the metal fragment. The complexes that display columnar mesomorphism are those that support more than one triphenylene per molecule or those that produce a similar effect by dipole–dipole interactions between the metal groups. These circumstances improve the balance of favorable enthalpic interactions versus unfavorable entropic contributions into a columnar stacking. Hybrid inorganic/organic dual columnar mesophases with high SCLC hole mobility along the columnar stacking, above 1 cm2 V–1 s–1, have been found. It is worth noting that the dicyanoplatinum complex displays mesophase phosphorescence based on Pt···Pt interactions.Ministerio de Ciencia e Innovación (Proyect CTQ2014-52796-P

Spin-crossover, mesomorphic and thermoelectrical properties of cobalt(II) complexes with alkylated N3-Schiff bases

Three new cobalt(ii) complexes, [Co(L12)2](BF4)2 (1), [Co(L14)2](BF4)2·H2O (2) and [Co(L16)2](BF4)2·H2O (3), where L12-16 are N3-Schiff bases appended with linear C12-16 carbon chains at the nitrogen atoms, were obtained in good yields by facile one-pot reactions. The single crystal X-ray structure of complex 1 shows a tetragonally compressed CoN6 coordination geometry. The melting temperatures of 1-3 were lower than 373 K, while their decomposition temperatures were above 473 K. All complexes have high-spin Co(ii) centres at 300 K and exhibit a columnar mesophase above 383 K. Complexes 1 and 3 showed normal thermal spin-crossover behaviour with weak hysteresis loops at about 320 K. Hence, these complexes showed uncoupled phase transitions (class iiia). The values for the Seebeck coefficient (Se) of the cobalt redox couples formed from 1 and 2 were 1.89 ± 0.02 mV K-1 and 1.92 ± 0.08 mV K-1, respectively, identifying them as potential thermoelectrochemical materials

Metal-directed columnar phase formation in tetrahedral zinc(II) and manganese(II) metallomesogens

New, non-discoid M(II) complexes [MCl2(L)] {M = Mn, Zn; L = 2,6-diformyl-4- methylphenolbis[3’,4’,5’-tris(hexadecyloxy)phenylimine]} have been prepared and shown to exhibit columnar mesophases, the nature of which was found to be metal-dependent. As analysed by DSC and small-angle X-ray diffraction experiments, the complex [ZnCl2(L)] exhibits a single mesophase with rectangular symmetry (Colr) between 46 and 145 °C, whereas the Mn(II) analogue [MnCl2(L)] displays a purely hexagonal mesophase (Colh) phase between 55 and 285 °C. By combining these results with those obtained from dilatometry, a model for the molecular organisation within the columnar mesophases is proposed. The single-crystal X-ray structure of the related complex [Zn(NO3)(L’)2]NO3.3MeOH {L’ = 2,6-diformyl-4-methylphenolbis[3’,4’,5’-tris(methoxy)phenylimine]} has been determined and supports the proposed mode of binding of the ligand to the metal via only one imine and a phenol

Host-Guest Complexation of [60]Fullerenes and Porphyrins Enabled by “Click Chemistry”

Herein the synthesis, characterization, and organization of a first-generation dendritic fulleropyrrolidine bearing two pending porphyrins are reported. Both the dendron and the fullerene derivatives were synthesized by Cu(I) -catalyzed alkyne-azide cycloaddition (CuAAC). The electron-donor-acceptor conjugate possesses a shape that allows the formation of supramolecular complexes by encapsulation of C60 within the jaws of the two porphyrins of another molecule. The interactions between the two photoactive units (i.e., C60 and Zn-porphyrin) were confirmed by cyclic voltammetry as well as by steady-state and time-resolved spectroscopy. For example, a shift of about 85 mV was found for the first reduction of C60 in the electron-donor-acceptor conjugate compared with the parent molecules, which indicates that C60 is included in the jaws of the porphyrin. The fulleropyrrolidine compound exhibits a rich polymorphism, which was corroborated by AFM and SEM. In particular, it was found to form supramolecular fibrils when deposited on substrates. The morphology of the fibrils suggests that they are formed by several rows of fullerene-porphyrin complexes

Green-blue light-emitting platinum(II) complexes of cyclometallated 4,6-difluoro-1,3-dipyridylbenzenes showing mesophase organisation

Blue-green light-emitting phosphorescent Pt-II complexes of 1,3-bis(2-pyridyl) benzene are reported that incorporate hexadecyl-containing fragments in the 5-position of the pyridine rings. Along with the more classical half disc-shaped hexacatenar molecule with six pendant alkoxy chains, which shows an R (3) over barm mesophase, the simpler complex functionalised by just two alkoxy chains, one at each pyridyl 5-position, was also found to be mesomorphic. The luminescence of pure films obtained from these complexes is orange-red, dominated by the excimer-like emission, and is independent of the thermal history of the film. The mesophases of the complexes are three-dimensional and columnar in nature - all are based on a two-dimensional hexagonal arrangement extended into the third dimension

Comparative Analysis of Self-Aggregation of Liquid Crystalline Pt(II) Complexes in Solution and in Neat Films

Two novel cycloplatinated complexes that differ by the presence/absence of a lateral fused cyclopenteno ring, respectively, were prepared. Although contributing to only a few percentage of the whole molecular volume, the presence of this aliphatic protuberance appears to be essential for the emergence of liquid crystalline behaviour. This pair of two similar compounds, non-mesomorphic complex and mesomorphic complex, was prepared as a model to assess the possible link of the self-aggregation in solution with the appearance of the liquid crystallinity in molten state. NMR dilution studies in CDCl3 solution and X-ray diffusion study in neat films show qualitative similarity of the aggregated structures formed by liquid crystalline complex. Solution studies may therefore be a useful additional tool to the characterization of the liquid crystalline properties and other self-association processes of Pt(II) complexes. © 2021We thank Northumbria University, CNRS, University of Strasbourg and Russian Foundation for Basic Research (project No. 18-03-00232A ) for the support of this work

Methicillin-Susceptible ST398 Staphylococcus aureus Responsible for Bloodstream Infections: An Emerging Human-Adapted Subclone?

In the course of an annual 3-month bloodstream infections (BSI) survey conducted during a four-year period in 31 healthcare institutions located in three noncontiguous French regions, we report 18 ST398 Staphylococcus aureus BSI. ST398 BSI incidence showed a seven-fold increase during the study period (0.002 per 1,000 patient days in 2007 vs. 0.014 in 2010). ST398 BSI isolates differed from the pig-borne multiresistant clone: 17/18 BSI isolates were methicillin susceptible and none was of t011, t034 or t108 pig-borne spa-types. ST398 BSI isolates had homogenous resistance patterns (15/18 with only Eryr) and prophagic content (all harboured the hlb-converting Sau3int phage). The clustering of BSI and pig-borne isolates by spa-typing and MLVA, the occurrence of Sau3int phage in BSI isolates and the lack of this phage in pig-borne isolates suggest that the emergence of BSI isolates could have arisen from horizontal transfer, at least of the Sau3int phage, in genetically diverse MSSA ST398 isolates. The acquisition of the phage likely plays a role in the increasing ability of the lysogenic ST398 isolates to colonize human. The mode of acquisition of the non pig-borne ST398 isolates by our 18 patients remains unclear. ST398 BSI were diagnosed in patients lacking livestock exposure and were significantly associated with digestive portals of entry (3/18 [16.7%] for ST398 vs. 19/767 [2.5%] for non ST398 BSI; p = .012). This raises the question of possible foodborne human infections. We suggest the need for active surveillance to study and control the spread of this human-adapted subclone increasingly isolated in the hospital setting

CC8 MRSA Strains Harboring SCCmec Type IVc are Predominant in Colombian Hospitals

BACKGROUND: Recent reports highlight the incursion of community-associated MRSA within healthcare settings. However, knowledge of this phenomenon remains limited in Latin America. The aim of this study was to evaluate the molecular epidemiology of MRSA in three tertiary-care hospitals in Medellín, Colombia. METHODS: An observational cross-sectional study was conducted from 2008-2010. MRSA infections were classified as either community-associated (CA-MRSA) or healthcare-associated (HA-MRSA), with HA-MRSA further classified as hospital-onset (HAHO-MRSA) or community-onset (HACO-MRSA) according to standard epidemiological definitions established by the U.S. Centers for Disease Control and Prevention (CDC). Genotypic analysis included SCCmec typing, spa typing, PFGE and MLST. RESULTS: Out of 538 total MRSA isolates, 68 (12.6%) were defined as CA-MRSA, 243 (45.2%) as HACO-MRSA and 227 (42.2%) as HAHO-MRSA. The majority harbored SCCmec type IVc (306, 58.7%), followed by SCCmec type I (174, 33.4%). The prevalence of type IVc among CA-, HACO- and HAHO-MRSA isolates was 92.4%, 65.1% and 43.6%, respectively. From 2008 to 2010, the prevalence of type IVc-bearing strains increased significantly, from 50.0% to 68.2% (p = 0.004). Strains harboring SCCmec IVc were mainly associated with spa types t1610, t008 and t024 (MLST clonal complex 8), while PFGE confirmed that the t008 and t1610 strains were closely related to the USA300-0114 CA-MRSA clone. Notably, strains belonging to these three spa types exhibited high levels of tetracycline resistance (45.9%). CONCLUSION: CC8 MRSA strains harboring SCCmec type IVc are becoming predominant in Medellín hospitals, displacing previously reported CC5 HA-MRSA clones. Based on shared characteristics including SCCmec IVc, absence of the ACME element and tetracycline resistance, the USA300-related isolates in this study are most likely related to USA300-LV, the recently-described 'Latin American variant' of USA300