Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Lipophilic Re(CO)₃pyca complexes for Mid-IR imaging applications.

ABSTRACT: Several Re(i)pyca conjugates incorporating long aliphatic amines have been synthesized through a one-pot methodology. The compounds have been fully characterized, and seven compounds have been structurally elucidated by single crystal X-ray diffraction. The C14 variant was probed as a potential organometallic IR dye. Large unilamellar vesicles were generated with DOPC and the C14 compound and we observed incorporation of the rhenium complex as observed by FTIR microscopy.

SUBMITTER: Schrage BR

PROVIDER: S-EPMC7932017 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Lipophilic Re(CO)3pyca complexes for Mid-IR imaging applications.

Schrage Briana R BR Frisinger Baylee R BR Schmidtke Sobeck Sarah J SJ Ziegler Christopher J CJ

Dalton transactions (Cambridge, England : 2003) 20210101 3

Several Re(i)pyca conjugates incorporating long aliphatic amines have been synthesized through a one-pot methodology. The compounds have been fully characterized, and seven compounds have been structurally elucidated by single crystal X-ray diffraction. The C14 variant was probed as a potential organometallic IR dye. Large unilamellar vesicles were generated with DOPC and the C14 compound and we observed incorporation of the rhenium complex as observed by FTIR microscopy. ...[more]

PMID: 33367427

Similar Datasets

Systematic investigation of CO2 : NH3 ice mixtures using mid-IR and VUV spectroscopy - part 1: thermal processing.

Project description:The adjustment of experimental parameters in interstellar ice analogues can have profound effects on molecular synthesis within an ice system. We demonstrated this by systematically investigating the stoichiometric mixing ratios of CO2 : NH3 ices as a function of thermal processing using mid-IR and VUV spectroscopy. We observed that the type of CO2 bonding environment was dependent on the different stoichiometric mixing ratios and that this pre-determined the NH3 crystallite structure after phase change. The thermal reactivity of the ices was linked to the different chemical and physical properties of the stoichiometric ratios. Our results provide new details into the chemical and physical properties of the different stoichiometric CO2 : NH3 ices enhancing our understanding of the thermally induced molecular synthesis within this ice system.

| S-EPMC9057146 | biostudies-literature

(8-Amino)quinoline and (4-Amino)phenanthridine Complexes of Re(CO)3 Halides.

Project description:In this report, we present a study on the synthesis, structure, and electronics of a series of (8-amino)quinoline and (4-amino)phenanthridine complexes of Re(CO)3X, where X = Cl and Br. In all cases, the (amino)heterocycles bind as bidentate ligands, with surprisingly symmetric modes of binding based on Re-N bond lengths. Between the complexes of (8-amino)quinolines and (4-amino)phenanthridines studied in this report, we do not observe much structural variation, and remarkably similar UV-visible absorption spectra. Expansion of the π-system in the (4-amino)phenanthridine complexes does result in an increase in the intensity of the lowest energy transitions (λmax), which computational modeling suggests are more purely MLCT in character compared with the mixed π-π*/MLCT character of these transitions in the smaller (8-amino)quinoline-supported complexes. DFT and TDDFT modeling further showed that consideration of spin-orbit coupling (SOC) is essential; omitting SOC misses the π-π* contributions to λmax and is unable to accurately model the observed electronic absorption spectra.

| S-EPMC7442205 | biostudies-literature

Di-Zinc-Aryl Complexes: CO2 Insertions and Applications in Polymerisation Catalysis.

Project description:Two new di-zinc-aryl complexes, [LZn2 Ph2 ] and [LZn2 (C6 F5 )2 ], coordinated by a diphenol tetraamine macrocyclic ligand have been prepared and fully characterised, including by single-crystal X-ray diffraction experiments. The complexes' reactivities with monomers including carbon dioxide, cyclohexene oxide, phthalic anhydride, isopropanol and phenol were investigated using both experimental studies and density functional theory calculations. In particular, [LZn2 Ph2 ] readily inserts carbon dioxide to form a carboxylate, at 1 bar pressure, whereas [LZn2 (C6 F5 )2 ] does not react. Under these conditions [LZn2 Ph2 ] shows moderate activity in the ring-opening copolymerisation of cyclohexene oxide/carbon dioxide (TOF=20 h-1 ), cyclohexene oxide/phthalic anhydride (TOF=33 h-1 ) and the ring-opening polymerisations of rac-lactide (TOF=99 h-1 ) and ϵ-caprolactone (TOF=5280 h-1 ).

| S-EPMC5488170 | biostudies-literature

In vivo O2 imaging in hepatic tissues by phosphorescence lifetime imaging microscopy using Ir(III) complexes as intracellular probes.

Project description:Phosphorescence lifetime imaging microscopy (PLIM) combined with an oxygen (O2)-sensitive luminescent probe allows for high-resolution O2 imaging of living tissues. Herein, we present phosphorescent Ir(III) complexes, (btp)2Ir(acac-DM) (Ir-1) and (btp-OH)3Ir (Ir-2), as useful O2 probes for PLIM measurement. These small-molecule probes were efficiently taken up into cultured cells and accumulated in specific organelles. Their excellent cell-permeable properties allowed for efficient staining of three-dimensional cell spheroids, and thereby phosphorescence lifetime measurements enabled the evaluation of the O2 level and distribution in spheroids, including the detection of alterations in O2 levels by metabolic stimulation with an effector. We took PLIM images of hepatic tissues of living mice by intravenously administrating these probes. The PLIM images clearly visualized the O2 gradient in hepatic lobules with cellular-level resolution, and the O2 levels were derived based on calibration using cultured cells; the phosphorescence lifetime of Ir-1 gave reasonable O2 levels, whereas Ir-2 exhibited much lower O2 levels. Intravenous administration of NH4Cl to mice caused the hepatic tissues to experience hypoxia, presumably due to O2 consumption to produce ATP required for ammonia detoxification, suggesting that the metabolism of the probe molecule might affect liver O2 levels.

| S-EPMC7713648 | biostudies-literature

CO2 capture by Mn(i) and Re(i) complexes with a deprotonated triethanolamine ligand.

Project description:CO2 capture at low concentration by catalysts is potentially useful for developing photocatalytic and electrocatalytic CO2 reduction systems. We investigated the CO2-capturing abilities of two complexes, fac-Mn(X2bpy)(CO)3(OCH2CH2NR2) and fac-Re(X2bpy)(CO)3(OCH2CH2NR2) (X2bpy = 4,4'-X2-2,2-bipyridine and R = -CH2CH2OH), which work as efficient catalysts for CO2 reduction. Both complexes could efficiently capture CO2 even from Ar gas containing only low concentration of CO2 such as 1% to be converted into fac-M(X2bpy)(CO)3(OC(O)OCH2CH2NR2) (M = Mn and Re). These CO2-capturing reactions proceeded reversibly and their equilibrium constants were >1000. The substituents of X2bpy strongly affected the CO2-capturing abilities of both Mn and Re complexes. The density functional theory (DFT) calculation could be used to estimate the CO2-capturing abilities of the metal complexes in the presence of triethanolamine.

| S-EPMC6429607 | biostudies-literature

Microporous Polymelamine Framework Functionalized with Re(I) Tricarbonyl Complexes for CO2 Absorption and Reduction.

Project description:A mixture of polymeric complexes based on the reaction between Re(CO)5Cl and the porous polymeric network coming from the coupling of melamine and benzene-1,3,5-tricarboxaldehyde was obtained and characterized by FTIR, NMR, SEM, XPS, ICP, XRD, and cyclic voltammetry (CV). The formed rhenium-based porous hybrid material reveals a noticeable capability of CO2 absorption. The gas absorption amount measured at 295 K was close to 44 cm3/g at 1 atm. An interesting catalytic activity for CO2 reduction reaction (CO2RR) is observed, resulting in a turn over-number (TON) close to 6.3 under 80 min of test at -1.8 V vs. Ag/AgCl in a TBAPF6 0.1 M ACN solution. A possible use as filler in membranes or columns can be envisaged.

| S-EPMC9782493 | biostudies-literature

Pyridylbenzimidazole based Re(i)(CO)3 complexes: antimicrobial activity, spectroscopic and density functional theory calculations.

Project description:fac-[ReBr(CO)3(L1,2)] L1 = 1-ethyl-2-(pyridin-2-yl)benzimidazole (1) and L2 = 1-[(pyridin-2-yl) benzimidazole]-propyl-sulfonic acid (2), fac-[Re2Br2(CO)6L3] (3) L3 = 1,1'-(hexane-1,6-diyl)bis[2-(pyridin-2-yl)1H-benzimidazole] and fac-[ReBr(CO)3(L4,5-κ2N1N2)] (L4 = 2,6-bis(benzimidazol-2'-yl)pyridine (4) and L5 = 2,6-bis(1-ethyl-benzimidazol-2'-yl)pyridine (5) were synthesized and fully characterized using different spectrocopic and analytical tools. The spectrocopic data showed coordination of L1-3 to fac-ReBr(CO)3 via the benzimidazole and pyridine N-atoms. For 4 and 5, the absence of a two-fold axis of symmetry for L4,5 in the 1H NMR spectra reflect the κ2N1,N2 mode of coordination. The electronic properties of 1-5 were investigated by time-dependent density functional theory calculations in the singlet and triplet states. The ligands and their Re(i) complexes were assessed for their potential antimicrobial activity. Compound 5 was screened against non-malignant cell line (noncancerous human embryonic kidney cell line (HEK293)) as well as evaluated for its blood compatibility.

| S-EPMC9064247 | biostudies-literature

Systematic investigation of CO2 : NH3 ice mixtures using mid-IR and VUV spectroscopy - part 2: electron irradiation and thermal processing.

Project description:Many experimental parameters determine the chemical and physical properties of interstellar ice analogues, each of which may influence the molecular synthesis that occurs in such ices. In part 1, James et al., RSC Adv., 2020, 10, 37517, we demonstrated the effects that the stoichiometric mixing ratio had on the chemical and physical properties of CO2 : NH3 mixtures and the impact on molecular synthesis induced by thermal processing. Here, in part 2, we extend this to include 1 keV electron irradiation at 20 K of several stoichiometric mixing ratios of CO2 : NH3 ices followed by thermal processing. We demonstrate that not all stoichiometric mixing ratios of CO2 : NH3 ice form the same products. Not only did the 4 : 1 ratio form a different residue after thermal processing, but O3 was observed after electron irradiation at 20 K, which was not observed in the other ratios. For the other ratios, the residue formed from a thermal reaction similar to the work shown in Part 1. However, conversion of ammonium carbamate to carbamic acid was hindered due to electron irradiation at 20 K. Our results demonstrate the need to systematically investigate stoichiometric mixing ratios to better characterise the chemical and physical properties of interstellar ice analogues to further our understanding of the routes of molecular synthesis under different astrochemical conditions.

| S-EPMC9042239 | biostudies-literature

Electronic Effects of Substituents on fac-M(bpy-R)(CO)3 (M = Mn, Re) Complexes for Homogeneous CO2 Electroreduction.

Project description:Synthesis and characterization of 14 new 2,2'-bipyridine metal complexes fac-M(bpy-R)(CO)3X (where M = Mn, X = Br or M = Re, X = Cl and R = -CF3, -CN, -Ph, -PhOH, -NMe2) are reported. The complexes have been characterized by NMR, IR spectroscopy and elemental analysis. Single crystal X-Ray diffraction structures have been solved for Re(dpbpy)(CO)3Cl (dpbpy = 4,6-diphenyl-2,2'-bipyridine) and Re(hpbpy)(CO)3Cl (hpbpy = 4-(2-hydroxy-phenyl)-6-phenyl-2,2'-bipyridine). Electrochemical behaviors of the complexes in acetonitrile under Ar and their catalytic performances for CO2 reduction with added water and MeOH have been investigated by cyclic voltammetry and controlled potential electrolysis. The role of the substituents on the electrochemical properties and the related over potentials required for CO2 transformation have been analyzed. The complexes carrying only electron withdrawing groups like -CF3, -CN totally lose their catalytic activities toward CO2 reduction, whereas the symmetric -NMe2 substituted and push-pull systems (containing both -NMe2 and -CF3) still display electrocatalytic current enhancement under CO2 atmosphere. The complexes carrying a phenyl or a phenol group in position 4 show catalytic behaviors similar to those of simple M-bpy systems. The only detected reduction product by GC analysis is CO: for example, fac-Re (bpy-4,4'-NMe2)(CO)3Cl gives CO with high faradic efficiency and a TON of 18 and 31, in absence of external proton source and with 5% MeOH, respectively. DFT calculations were carried out to highlight the electronic properties of the complexes; results are in agreement with experimental electrochemical data.

| S-EPMC6561311 | biostudies-literature

Fluoro Nitrenoid Complexes FN=MF2 (M=Co, Rh, Ir): Electronic Structure Dichotomy and Formation of Nitrido Fluorides N≡MF3.

Project description:The fluoronitrenoid metal complexes FNCoF2 and FNRhF2 as well as the first ternary RhVI and IrVI complexes NIrF3 and NRhF3 are described. They were obtained by the reaction of excited Group-9 metal atoms with NF3 and their IR spectra, isolated in solid rare gases (neon and argon), were recorded. Aided by the observed 14/15 N isotope shifts and quantum-chemical predictions, all four stretching fundamentals of the novel complexes were safely assigned. The F-N stretching frequencies of the fluoronitrenoid complexes FNCoF2 (1056.8 cm-1 ) and FNRhF2 (872.6 cm-1 ) are very different and their N-M bonds vary greatly. In FNCoF2 , the FN ligand is singly bonded to Co and bears considerable iminyl/nitrene radical character, while the N-Rh bond in FNRhF2 is a strong double bond with comparatively strong σ- and π-bonds. The anticipated rearrangement of FNCoF2 to the nitrido CoVI complex is predicted to be endothermic and was not observed.

| S-EPMC7756499 | biostudies-literature