skip to main content

Explore Research Products in the NSF-PAR

Title: Inorganic clusters as metalloligands: ligand effects on the synthesis and properties of ternary nanopropeller clusters
Redox-active multimetallic platforms with synthetically addressable and hemilabile active sites are attractive synthetic targets for mimicking the reactivity of enzymatic co-factors toward multielectron transformations. To this end, a family of ternary clusters featuring three edge metal sites anchored on a [Co 6 Se 8 ] multimetallic support via amidophosphine ligands are a promising platform. In this report, we explore how small changes in the stereoelectronic properties of these ligands alter [Co 6 Se 8 ] metalloligand formation, but also substrate binding affinity and strength of the edge/support interaction in two new ternary clusters, M 3 Co 6 Se 8 L 6 (M = Zn, Fe; L (−) = Ph 2 PN (−)i Pr). These clusters are characterized extensively using a range of methods, including single crystal X-ray diffraction, electronic absorption spectroscopy and cyclic voltammetry. Substrate binding studies reveal that Fe 3 Co 6 Se 8 L 6 resists coordination of larger ligands like pyridine or tetrahydrofuran, but binds the smaller ligand CN t Bu. Additionally, investigations into the synthesis of new [Co 6 Se 8 ] metalloligands using two aminophosphines, Ph 2 PN(H) i Pr (L H ) and i Pr 2 PN(H) i Pr, led to the synthesis and characterization of Co 6 Se 8 L H 6 , as well as the smaller clusters Co 4 Se 2 (CO) 6 L H 4 , Co 3 Se(μ 2 -PPh 2 )(CO) 4 L H 3 , and [Co(CO) 3 ( i Pr 2 PN(H) i Pr)] 2 . Cumulatively, this study expands our understanding on the effect of the stereoelectronic properties of aminophosphine ligands in the synthesis of cobalt chalcogenide clusters, and, importantly on modulating the push–pull dynamic between the [Co 6 Se 8 ] support, the edge metals and incoming coordinating ligands in ternary M 3 Co 6 Se 8 L 6 clusters.  more » « less
Award ID(s):
1944843
NSF-PAR ID:
10212253
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Dalton Transactions
Volume:
49
Issue:
45
ISSN:
1477-9226
Page Range / eLocation ID:
16464 to 16473
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ( , USENIX annual technical conference)
    A s a c om pl e men t t o da ta d edupli cat ion , de lta c om p ress i on fu r- t he r r edu c es t h e dat a vo l u m e by c o m pr e ssi n g n o n - dup li c a t e d ata chunk s r e l a t iv e to t h e i r s i m il a r chunk s (bas e chunk s). H ow ever, ex is t i n g p o s t - d e dup li c a t i o n d e l t a c o m pr e ssi o n a p- p ro a ches fo r bac kup s t or ag e e i t h e r su ffe r f ro m t h e l ow s i m - il a r i t y b e twee n m any de te c ted c hun ks o r m i ss so me po t e n - t i a l s i m il a r c hunks , o r su ffer f r om l ow (ba ckup and r es t ore ) th r oug hpu t du e t o extr a I/ Os f or r e a d i n g b a se c hun ks o r a dd a dd i t i on a l s e r v i c e - d i s r up t ive op e r a t i on s to b a ck up s ys t em s. I n t h i s pa p e r, w e pr opo se L oop D e l t a t o a dd ress the above - m e n t i on e d prob l e m s by an e nha nced em b e ddi n g d e l t a c o m p - r e ss i on sc heme i n d e dup li c a t i on i n a non - i n t ru s ive way. T h e e nha nce d d elt a c o mpr ess ion s che m e co m b in e s f our key t e c h - ni qu e s : (1) du a l - l o c a li t y - b a s e d s i m il a r i t y t r a c k i n g to d e t ect po t e n t i a l si m il a r chun k s b y e x p l o i t i n g both l o g i c a l and ph y - s i c a l l o c a li t y, ( 2 ) l o c a li t y - a wa r e pr e f e t c h i n g to pr efe tc h ba se c hun ks to a vo i d ex t ra I/ Os fo r r e a d i n g ba s e chun ks on t h e w r i t e p at h , (3) c a che -aware fil t e r to avo i d ext r a I/Os f or b a se c hunk s on t he read p at h, a nd (4) i nver sed de l ta co mpressi on t o perf orm de lt a co mpress i o n fo r d at a chunk s t hat a re o th e r wi se f o r b i dd e n to s er ve as ba se c hunk s by r ew r i t i n g t e c hn i qu e s d e s i g n e d t o i m p r ove r es t o re pe rf o rma nc e. E x p e r i m e n t a l re su lts indi ca te t hat L oop D e l t a i ncr ea se s t he c o m pr e ss i o n r a t i o by 1 .2410 .97 t i m e s on t op of d e dup li c a - t i on , wi t hou t no t a b l y a ffe c t i n g th e ba ck up th rou ghpu t, a nd i t i m p r ove s t he res to re p er fo r m an ce b y 1.23.57 t i m e 
    more » « less
  2. ; ; ; ; ; ; ( , Chemical Science)
    null (Ed.)
    Tuning the properties of atomic crystals in the two-dimensional (2D) limit is synthetically challenging, but critical to unlock their potential in fundamental research and nanotechnology alike. 2D crystals assembled using superatomic blocks could provide a route to encrypt desirable functionality, yet strategies to link the inorganic blocks together in predetermined dimensionality or symmetry are scarce. Here, we describe the synthesis of anisotropic van der Waals crystalline frameworks using the designer superatomic nanocluster Co 3 (py) 3 Co 6 Se 8 L 6 (py = pyridine, L = Ph 2 PN(Tol)), and ditopic linkers. Post-synthetically, the 3D crystals can be mechanically exfoliated into ultrathin flakes (8 to 60 nm), or intercalated with the redox-active guest tetracyanoethylene in a single-crystal-to-single-crystal transformation. Extensive characterization, including by single crystal X-ray diffraction, reveals how intrinsic features of the nanocluster, such as its structure, chirality, redox-activity and magnetic profile, predetermine key properties of the emerging 2D structures. Within the nanosheets, the strict and unusual stereoselectivity of the nanocluster's Co edges for the low symmetry (α,α,β) isomer gives rise to in-plane structural anisotropy, while the helically chiral nanoclusters self-organize into alternating Δ- and Λ-homochiral rows. The nanocluster's high-spin Co edges, and its rich redox profile make the nanosheets both magnetically and electrochemically active, as revealed by solid state magnetic and cyclic voltammetry studies. The length and flexibility of the ditopic linker was varied, and found to have a secondary effect on the structure and stacking of the nanosheets within the 3D crystals. With these results we introduce a deterministic and versatile synthetic entry to programmable functionality and symmetry in 2D superatomic crystals. 
    more » « less
  3. ; ; ; ( , ChemPhysChem)
    Abstract

    Herein, we report on the synthesis of ultrasmall Pd nanoclusters (∼2 nm) protected by L‐cysteine [HOCOCH(NH2)CH2SH] ligands (Pdn(L‐Cys)m) and supported on the surfaces of CeO2, TiO2, Fe3O4, and ZnO nanoparticles for CO catalytic oxidation. The Pdn(L‐Cys)mnanoclusters supported on the reducible metal oxides CeO2, TiO2and Fe3O4exhibit a remarkable catalytic activity towards CO oxidation, significantly higher than the reported Pd nanoparticle catalysts. The high catalytic activity of the ligand‐protected clusters Pdn(L‐Cys)mis observed on the three reducible oxides where 100 % CO conversion occurs at 93–110 °C. The high activity is attributed to the ligand‐protected Pd nanoclusters where the L‐cysteine ligands aid in achieving monodispersity of the Pd clusters by limiting the cluster size to the active sub‐2‐nm region and decreasing the tendency of the clusters for agglomeration. In the case of the ceria support, a complete removal of the L‐cysteine ligands results in connected agglomerated Pd clusters which are less reactive than the ligand‐protected clusters. However, for the TiO2and Fe3O4supports, complete removal of the ligands from the Pdn(L‐Cys)mclusters leads to a slight decrease in activity where the T100%CO conversion occurs at 99 °C and 107 °C, respectively. The high porosity of the TiO2and Fe3O4supports appears to aid in efficient encapsulation of the bare Pdnnanoclusters within the mesoporous pores of the support.

     
    more » « less
  4. ; ; ; ( , Dalton Transactions)
    Three routes are explored to the title halide/cyanide complexes trans -Fe(CO)(NO)(X)(P((CH 2 ) 14 ) 3 P) ( 9c-X ; X = Cl/Br/I/CN), the Fe(CO)(NO)(X) moieties of which can rotate within the diphosphine cages (Δ H ‡ /Δ S ‡ (kcal mol −1 /eu −1 ) 5.9/−20.4 and 7.4/−23.9 for 9c-Cl and 9c-I from variable temperature 13 C NMR spectra). First, reactions of the known cationic complex trans -[Fe(CO) 2 (NO)(P((CH 2 ) 14 ) 3 P)] + BF 4 − and Bu 4 N + X − give 9c-Cl /- Br /- I /- CN (75–83%). Second, reactions of the acyclic complexes trans -Fe(CO)(NO)(X)(P((CH 2 ) m CHCH 2 ) 3 ) 2 and Grubbs’ catalyst afford the tris(cycloalkenes) trans -Fe(CO)(NO)(X)(P((CH 2 ) m CHCH(CH 2 ) m ) 3 P) ( m /X = 6/Cl,Br,I,CN, 7/Cl,Br, 8/Cl,Br) as mixtures of Z / E isomers (24–41%). Third, similar reactions of trans -[Fe(CO) 2 (NO)(P((CH 2 ) m CHCH 2 ) 3 ) 2 ] + BF 4 − and Grubbs’ catalyst afford crude trans -[Fe(CO) 2 (NO)P((CH 2 ) m CHCH(CH 2 ) m ) 3 P)] + BF 4 − ( m = 6, 8). However, the CC hydrogenations required to consummate routes 2 and 3 are problematic. Crystal structures of 9c-Cl /- Br /- CN are determined. Although the CO/NO/X ligands are disordered, the void space within the diphosphine cages is analyzed in terms of horizontal and vertical constraints upon Fe(CO)(NO)(X) rotation and the NMR data. The molecules pack in identical motifs with parallel P–Fe–P axes, and without intermolecular impediments to rotation in the solid state. 
    more » « less
  5. ; ; ; ( , Chemical Science)
    We report a rare example of oxygen atom transfer (OAT) from a polyoxometalate cluster to a series of tertiary phosphanes. Addition of PR 3 (PR 3 = PMe 3 , PMe 2 Ph, PMePh 2 , PPh 3 ) to a neutral methoxide-bridged polyoxovanadate-alkoxide (POV-alkoxide) cluster, [V 6 O 7 (OMe) 12 ] 0 , results in isolation of a reduced structure with phosphine oxide datively coordinated to a site-differentiated V III ion. A positive correlation between the steric and electronic properties of the phosphane and the reaction rate was observed. Further investigation of the steric influence of the alkoxy-bridged clusters on OAT was probed through the use of POV clusters with bridging alkoxide ligands of varying chain length ([V 6 O 7 (OR′) 12 ]; R′ = Et, n Pr). These investigations expose that steric hinderance of the vanadyl moieties has significant influence on the rate of OAT. Finally, we report the reactivity of the reduced POV-alkoxide clusters with styrene oxide, resulting in the deoxygenation of the substrate to generate styrene. This result is the first example of epoxide deoxygenation using homometallic polyoxometalate clusters, demonstrating the potential for mono-vacant Lindqvist clusters to catalyze the removal of oxygen atoms from organic substrates. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email