skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • Two polymorph modifications of tris(hexafluoroacetylacetonato)iron(III) revealed: is that common for other trivalent metals?
Title: Two polymorph modifications of tris(hexafluoroacetylacetonato)iron(III) revealed: is that common for other trivalent metals?
A long-standing issue about the correct identification of an important starting reagent, iron(III) hexafluoroacetylacetonate, Fe(hfac)3(1), has been resolved. Thetris-chelated mononuclear complex was found to crystallize in two polymorph modifications which can be assigned as the low-temperature (1-L) monoclinicP21/nand the high-temperature (1-H) trigonalP\overline{3}. Low-temperature polymorph1-Lwas found to transform to1-Hupon sublimation at 44 °C. Two modifications are clearly distinguished by powder X-ray diffraction (PXRD), single-crystal X-ray diffraction, differential scanning calorimetry (DSC), and melting-point measurements. On the other hand, the two forms share similar characteristics in direct analysis in real-time mass spectrometry (DART-MS), attenuated total reflection (ATR) spectroscopy, and some physical properties, such as color, volatility, sensitivity, and solubility. Analysis of the literature and some of our preliminary data strongly suggest that the appearance of two polymorph modifications for trivalent metal (both transition and main group) hexafluoroacetylacetonates is a common case for several largely used complexes not yet accounted for in the crystallographic databases.  more » « less
Award ID(s):
1834750 2400091 1955585
PAR ID:
10578244
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
International Union of Crystallography (co-published with Wiley)
Date Published:
Journal Name:
Acta Crystallographica Section C Structural Chemistry
Volume:
80
Issue:
9
ISSN:
2053-2296
Page Range / eLocation ID:
567 to 575
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; (, Chemistry – A European Journal)
    Abstract Here, the combination of theoretical computations followed by rapid experimental screening and in situ diffraction studies is demonstrated as a powerful strategy for novel compounds discovery. When applied for the previously “empty” Na−Zn−Bi system, such an approach led to four novel phases. The compositional space of this system was rapidly screened via the hydride route method and the theoretically predicted NaZnBi (PbClF type,P4/nmm) and Na11Zn2Bi5(Na11Cd2Sb5type,P) phases were successfully synthesized, while other computationally generated compounds on the list were rejected. In addition, single crystal X‐ray diffraction studies of NaZnBi indicate minor deviations from the stoichiometric 1 : 1 : 1 molar ratio. As a result, two isostructural (PbClF type,P4/nmm) Zn‐deficient phases with similar compositions, but distinctly different unit cell parameters were discovered. The vacancies on Zn sites and unit cell expansion were rationalized from bonding analysis using electronic structure calculations on stoichiometric “NaZnBi”.In‐situsynchrotron powder X‐ray diffraction studies shed light on complex equilibria in the Na−Zn−Bi system at elevated temperatures. In particular, the high‐temperature polymorphHT‐Na3Bi (BiF3type,Fmm) was obtained as a product of Na11Zn2Bi5decomposition above 611 K.HT‐Na3Bi cannot be stabilized at room temperature by quenching, and this type of structure was earlier observed in the high‐pressure polymorphHP‐Na3Bi above 0.5 GPa. The aforementioned approach of predictive synthesis can be extended to other multinary systems. 
    more » « less
  2. ; ; ; ; ; ; (, Angewandte Chemie International Edition)
    Abstract The imidophosphorane ligand, [NPtBu3]−(tBu=tert‐butyl), enables isolation of a pseudo‐tetrahedral, tetravalent praseodymium complex, [Pr4+(NPtBu3)4] (1‐Pr), which is characterized by a suite of physical characterization methods including single‐crystal X‐ray diffraction, electron paramagnetic resonance, and L3‐edge X‐ray near‐edge spectroscopies. Variable‐temperature direct‐current magnetic susceptibility data, supported by multiconfigurational quantum chemical calculations, demonstrate that the electronic structure diverges from the isoelectronic Ce3+analogue, driven by increased crystal field. The four‐coordinate environment around Pr4+in1‐Pr, which is unparalleled in reported extended solid systems, provides a unique opportunity to study the interplay between crystal field splitting and spin‐orbit coupling in a molecular tetravalent lanthanide within a pseudo‐tetrahedral coordination geometry. 
    more » « less
  3. ; ; ; ; ; ; ; ; (, Angewandte Chemie International Edition)
    Abstract We report on the largest open‐shell graphenic bilayer and also the first example of triply negatively charged radical π‐dimer. Upon three‐electron reduction, bilayer nanographene fragment molecule (C96H24Ar6)2(Ar=2,6‐dimethylphenyl) (12) was transformed to a triply negatively charged species123.−, which has been characterized by single‐crystal X‐ray diffraction, electron paramagnetic resonance (EPR) spectroscopy and magnetic properties on a superconducting quantum interference device (SQUID).123.−features a 96‐center‐3‐electron (96c/3e) pancake bond with a doublet ground state, which can be thermally excited to a quartet state. It consists of 34 π‐fused rings with 96 conjugatedsp2carbon atoms. Spin frustration is observed with the frustration parameterf>31.8 at low temperatures in123.−, which indicates graphene upon reduction doping may behave as a quantum spin liquid. 
    more » « less
  4. ; ; ; ; ; ; ; (, Angewandte Chemie International Edition)
    Abstract Whereas low‐temperature (−78 °C) reaction of the lithium dithiolene radical1.with boron bromide gives the dibromoboron dithiolene radical2., the parallel reaction of1.with (C6H11)2BCl (0 °C) affords the dicyclohexylboron dithiolene radical3.. Radicals2.and3.were characterized by single‐crystal X‐ray diffraction, UV/Vis, and EPR spectroscopy. The nature of these radicals was also probed computationally. Under mild conditions,3.undergoes unexpected thiourea‐mediated B−C bond activation to give zwitterion4, which may be regarded as an anionic dithiolene‐modified carbene complex of the sulfenyl cation RS+(R=cyclohexyl). 
    more » « less
  5. ; ; ; (, Chemistry – A European Journal)
    Abstract Affinities of six anions (mesylate, acetate, trifluoroacetate,p‐toluenecarboxylate,p‐toluenesulfonate, and perfluorooctanoate) for three related Pt2+‐linked porphyrin nanocages were measured to probe the influence of different noncovalent recognition motifs (e. g., hydrogen bonding, electrostatics, π bonding) on anion binding. Two new hosts of M6L312+(1b) and M4L28+(2) composition (M=(en)Pt2+, L=(3‐py)4porphyrin) were prepared in a one‐pot synthesis and allowed comparison of hosts that differ in structure while maintaining similar N−H hydrogen‐bond donor ability. Comparisons of isostructural hosts that differ in hydrogen‐bonding ability were made between1band a related M6L312+nanoprism (1a, M=(tmeda)Pt2+) that lacks N−H groups. Considerable variation in association constants (K1=1.6×103 M−1to 1.3×108 M−1) and binding mode (exovs.endo) were found for different host–guest combinations. Strongest binding was seen betweenp‐toluenecarboxylate and1b, but surprisingly, association of this guest with1awas only slightly weaker despite the absence of NH⋅⋅⋅O interactions. The high affinity betweenp‐toluenecarboxylate and1acould be turned off by protonation, and this behavior was used to toggle between the binding of this guest and the environmental pollutant perfluorooctanoate, which otherwise has a lower affinity for the host. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email