#fblockrocks

Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides - Nature Communications Although the trivalent actinides are similar to the lanthanide series in terms of chemistry and bonding, their structures and properties can diverge significantly. Here, the authors report a series of...

6 months ago

I remember seeing the americium crystals from like 20 ft away. Great job Nick! #fblockrocks www.nature.com/articles/s41...

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Molecular complexes of low-valent f-elements from lanthanum to californium This review outlines the structure and chemistry of divalent lanthanides and actinides in small molecule systems, focusing on the less accessible diva…

7 months ago

@hbwineinger.bsky.social wrote this review for those interested in low valent f elements #fblockrocks www.sciencedirect.com/science/arti...

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9 months ago

Neptunium (Np3+) has a beautiful alexandrite effect. Left is one lab, center is natural sunlight, and right is a lab under fluorescent lighting. 5f-5f transitions are magical. This is the same solution. Some great pics taken by @jp_brannon #fblockrocks #actinides

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Effects of the Inverse Trans-Influence in a Berkelium(III) Phosphine Oxide Complex An example of a 249Bk3+ phosphine oxide complex has been prepared to examine and quantify the effects of the inverse trans-influence (ITI) on a late actinide complex. This has been accomplished through a comparison of cis and trans Bk-ligand bonds in the meridional berkelium(III) complex, BkBr3(OPCy3)3 (OPCy3 = tricyclohexylphosphine oxide). A detailed bond metric analysis was completed that includes the shortest published distance for a Bk3+–O bond, attributed to the smaller coordination number of Bk3+ of six in mer-BkBr3(OPCy3)3. ITI calculations of the trans Bk3+–O bond provide an ITI value (98.5(2)%) comparable to that of mer-AmBr3(OPCy3)3 (98.2(2)%) and indicate a small 5f orbital contribution to bonding. This effect is discussed in the context of the isomorphous lanthanide(III) series where the ITI is calculated to be higher for mer-BkBr3(OPCy3)3 than in most Ln3+ analogues.

9 months ago

249Bk (t1/2 ~330 days) is a beta blasting bully, but sometimes things work out #fblockrocks #bkallday @teasactinides.bsky.social pubs.acs.org/doi/10.1021/...

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Unveiling the covalency of versatile Pu(iii)-N bonds in a unique plutonium(iii) complex A trivalent plutonium–pyrazinyl–tetrazolate complex Na2[Pu(Hdtp)(dtp)2(H2O)4]·9H2O (Pu_dtp, H2dtp = 2,3-di-1H-tetrazol-5-ylpyrazine) was synthesized through metathesis reaction of plutonium bromide an...

10 months ago

Plutonium chemistry is wack and this compound is another reason to provide evidence towards that #fblockrocks @teasactinides.bsky.social
pubs.rsc.org/en/content/a...

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@simonschemie.bsky.social

1 year ago

I’ll never get used to this. From left to right: John Wagner, Director of Idaho National Laboratory. Katy Huff, former assistant secretary for nuclear energy. Some random guy they grabbed off a hiking trail. Rita Baranwal, VP at Westinghouse #AAAS #nuclear #fblockrocks #ChemSky

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Simon Obrusnik

1 year ago

Yesterday I saw a smudge of Californium-252 (Electroplated on Titantium) for the first time of my life! ☢️
I am really looking forward to making a Video about it :D
Hopefully in the future I get to see these elements in quantities where I can see their colour 😁
#fblockrocks #californium

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High-Pressure Effects on an Octa-Hydrated Curium Complex: An Experimental and Theoretical Investigation An octa-hydrated curium compound [Cm(H2O)8](Hdtp)(dtp)·H2O (Cm1, H2dtp = 2,3-di(tetrazol-5-yl)pyrazine) along with its lanthanide analogues [Ln(H2O)8](Hdtp)(dtp)·H2O (Ln1, Ln3+ = La3+–Nd3+, Sm3+–Lu3+)...

1 year ago

I am super proud of this paper. It was a massive, multi-year undertaking by three different groups. If you've ever wanted to understand the high-pressure behavior of curium, here it is. @gagliardilaura.bsky.social #fblockrocks #nuclear #chemsky #bluesci #highpressure
pubs.acs.org/doi/full/10....

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1 year ago

As we move to higher pressures centering samples by hand in diamond anvil cells is no longer possible. Meet our new micromanipulator. The hole on the screen is only 70 microns in diameter. #chemsky #bluesci #fblockrocks #highpressure #nuclear

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1 year ago

Using Pu-242 has resulted in some of the best colors I’ve ever seen as a chemist. 🤩

@realtimechem.bsky.social @berkeleylab.lbl.gov

#plutonium #realtimechem #fblockrocks #radiochemistry

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1 year ago

I love pictures of clean californium. This small quantity has enough gamma radiation to give you your annual background dose in ~30 minutes on contact pictured here is the oxalate #fblockrocks

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Isolation of Inner-Sphere Aquo Complexes of Samarium(II) The cis-anti-cis and cis-syn-cis isomers of [Sm(dicyclohexano-18-crown-6)(H2O)2]I2 exhibiting trans water molecules bound to the Sm2+ ion have been isolated and characterized. Sm2+ possesses an electrochemical potential sufficient for water reduction, and thus these complexes add to the recent body of evidence that the oxidation of Sm2+ by water can operate by a mechanism that is not straightforward. These complexes are obtained by the direct addition of stoichiometric amounts of water to solutions of the respective Sm(dicyclohexano-18-crown-6)I2 isomers under an inert atmosphere. The parent complex, Sm(dicyclohexano-18-crown-6)I2, lacking coordinating water molecules can be obtained through rigorous exclusion of water. It was determined that the bulky cyclohexano-substituents deter intramolecular interactions between [Sm(dicyclohexano-18-crown-6)(H2O)2]I2 complexes and slow the oxidization of the metal centers. The extent of the stability of these complexes to the presence of water has been further probed through cyclic voltammetry, where it was found that the redox potential of both isomers of [Sm(dicyclohexano-18-crown-6)(H2O)2]I2 maintains quasi-reversible behavior with a 50,000-fold excess of water to Sm2+ in solution with the cis-syn-cis complex being quasi-reversible at even higher concentrations of water. Solution-phase spectroscopy of these complexes in acetonitrile shows a corresponding hypsochromic shift of the Sm2+ 4f → 5d transition typically observed in the visible region from Sm2+ complexes. The crystalline compounds obtained in this study support solid-state spectroscopic trends observed from other Sm2+ crown-ether complexes containing iodide counterions, wherein the proximity of the iodide ions to the metal center determines whether the complex can exhibit 4f → 4f photoluminescence.

1 year ago

This article was years in the making. Did you think water could coordinate to Sm(II) without being reduced? Well it can. Congratulations Todd! #Chemsky #Bluesci #samarium #rareearths #fblockrocks

pubs.acs.org/doi/10.1021/...

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Daumann Lab

@daumannl.bsky.social

1 year ago

A Bar chart showing optical densities of bacterial cultures in the presence of differnet lanthanides. Promethium is included and fits well within its expected spot in the lanthanide series. In the right upper corner a comic of a cultivation flask with bacteria is shown.

Thats rad! Philippes first first author preprint is out: Lanthanide-dependent Methanotroph Thrives on Radioactive #Promethium #fblockrocks! doi.org/10.26434/che... We show that both the Ln-dependent enzyme MDH as well as strain SolV can use the beta-emitter Pm-147 in its metabolism. #chemsky 🧪

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1 year ago

How things have changed…25 years ago nuclear was dead. Now it’s proudly proclaimed. Even though the color has been altered for the banner, that cone vial contained a sample of actinium used in nuclear medicine. The sample glowed blue. #nuclear #actinium #fblockrocks #actinides #Chemsky #Bluesci

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Deviation between the Structural Chemistry of Barium and Radium Halides: Synthesis and Characterization of RaX2·H2O and RaX2·2H2O (X– = Cl– and Br–) To develop the structural chemistry of radium, the halide compounds RaX2·H2O and RaX2·2H2O (X– = Cl– and Br–) have been synthesized and characterized and serve as benchmarks for comparisons with more complex compounds in the future. In contrast with historic reports on the structural chemistry of radium, the Ra2+ chlorides differ from their Ba2+ analogues. For MCl2·H2O (M2+ = Ba2+, Ra2+), the variance between the metal coordination environments manifests as a small, local distortion that becomes more apparent in the extended structure. However, differences between RaCl2·2H2O and BaCl2·2H2O are more pronounced with a 10-coordinate Ra2+ cation being observed instead of a nine-coordinate Ba2+ in BaCl2·2H2O. RaBr2·nH2O (n = 1 or 2) are isomorphous with the Ba2+ analogues. Raman spectroscopy was used as an additional probe of these compounds and reveals substantial shifts and different vibrational modes between RaX2·H2O and RaX2·2H2O compared to BaX2·2H2O.

1 year ago

Super happy with this article. Ra-226 makes Cf-249 look cold. There's more radium chemistry to come after the holidays. #Chemsky #bluesci #radium #nuclear #fblockrocks
pubs.acs.org/doi/full/10....

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1 year ago

Some festive U-238 crystals. 🎄🎅✨

@realtimechem.bsky.social @berkeleylab.bsky.social

#fblockrocks #uranium #actinide #realtimechen #crystals

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Daumann Lab

@daumannl.bsky.social

1 year ago

Yes I could keep watching these forever 😅, 😍 awesome, thank you for the recipe of that one! Will try this for sure as it contains cerium, and lanthanides are my favorite elements #fblockrocks

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1 year ago

Hello Pu-242 💚✨

#realtimechem #actinides #fblockrocks #plutonium #crystals

@realtimechem.bsky.social @berkeleylab.bsky.social

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Structure, Covalency, and Paramagnetism of Homoleptic Actinide and Lanthanide Amidinate Complexes Isostructural trivalent lanthanide and actinide amidinates bearing the N,N’-bis(isopropyl)benzamidinate (iPr2BA) ligand [LnIII/AnIII(iPr2BA)3] (Ln = La, Nd, Sm, Eu, Yb, Lu; An = U, Np) have been synthesized and characterized in both solid and solution states. All compounds were examined in the solid state utilizing single crystal X-ray diffraction (SC-XRD), revealing a notable deviation in the actinide series with shortened bond lengths compared to the trend in the lanthanide series, suggesting a nonionic contribution to the actinide–ligand bonding. Quantum-chemical bonding analysis further elucidated the nature of these interactions, highlighting increased covalency within the actinide series, as evidenced by higher delocalization indices and greater 5f orbital occupation, except for Th(III) and Pa(III), which demonstrated substantial 6d orbital occupancies. An in-depth paramagnetic NMR study in solution also sheds light on the covalent character of actinide–ligand bonding, with the separation of pseudocontact (PCS) and contact shift (FCS) contributions employing the Bleaney and Reilley method. This analysis unveiled significant contact contributions in the actinide complexes, indicating enhanced covalency in actinide–ligand bonding. To corroborate these observations, an accurate PCS calculation method based on the Kuprov equation, incorporating both the distribution of electronic spin density and magnetic susceptibility obtained from CASSCF calculations, was applied and compared with experimental values.

1 year ago

Hi bluesky, meet blueplutonium #fblockrocks

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Daumann Lab

@daumannl.bsky.social

1 year ago

Lego Figure of a scientist (Sophie) with long brown hair holing a lego pipette sitting in front of a lego microbiology lab bench.

Here we further characterize methylolanthanin (MLL), a chelator that is involved in Ln metabolism in bacteria (see www.pnas.org/doi/10.1073/...) Yes, methylotrophic bacteria use La, Nd... in their C1 metabolism! #fblockrocks They use them in the active site of methanol dehydrogenase enzymes. Anyway…

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Peter Kaden

@kadenp.bsky.social

1 year ago

From earlier this year: If you're interested in #actinides and #felements check out Boseok's first and first author paper in InorgChem
#fblockrocks #NMRChat #chemsky #nuclear #openaccess
pubs.acs.org/doi/10.1021/...

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Peter Kaden

@kadenp.bsky.social

1 year ago

Comparative Analysis of Tetravalent Actinide Schiff Base Complexes: Influence of Donor and Ligand Backbone on Molecular Geometry and Metal Binding Novel tetravalent actinide (AnIV) compounds with the Schiff base ligand pyrophen, including the transuranium elements Np and Pu, are characterized in solid state and solution, as well as by quantum c...

Tamara's first paper dealing with a Comparative Analysis of Tetravalent Actinide SchiffBase Complexes: Influence of Donor and Ligand Backbone on Molecular Geometry and Metal Binding
#fblockrocks #NMRChat #chemsky #nuclear #openaccess
chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/...

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1 year ago

Ok, here's mine #chemsky. Should I have limited the number of entries? Pretty cool seeing so many #transuranium elements highlighted. #fblockrocks

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1 year ago

What a great way to end the week! U-238 crystals meet Bluesky 🥳🥹

#fblockrocks #chemsky #uranium #actinides

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Comprehensive Synthesis and Structural Trends in Tetramethyl Diglycolamide (TMDGA) Nitrate Complexes with Lanthanides and Americium Complexes of N,N,N′,N′-tetramethyl diglycolamide (TMDGA), a hydrophilic diglycolamide (DGA) proposed as an aqueous phase holdback reagent, have been crystallized for the majority of the lanthanide ser...

1 year ago

Diglycolamides are one of the most useful ligands for f-block separations. Really happy with B. Rotermund’s article on these complexes. #bluesci #chemsky #fblockrocks #americium #lanthanides #rareearths #nuclear

pubs.acs.org/doi/abs/10.1...

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