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1. L oo p D e l t a : E m b e dd i n g L o c a li t y - a w a r e O pp o r t un i s t i c D e l t a C o m p r e ss i o n i n I n li n e D e dup li c a t i o n f o r Hi g h l y E ffic i e n t D a t a R e du c t i o n

   Zhang, Yucheng ; Jiang, Hong ; Feng, Dan ; Jiang Nan ; Qui, Taorong ; Huang, Wei ( July 2023 , 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 

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2. Inorganic clusters as metalloligands: ligand effects on the synthesis and properties of ternary nanopropeller clusters

   https://doi.org/10.1039/D0DT02416C  

   Kephart, Jonathan A. ; Boggiano, Andrew C. ; Kaminsky, Werner ; Velian, Alexandra ( November 2020 , Dalton Transactions)

   null (Ed.)

   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. 

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3. Macrocyclic Complexes Derived from Four cis ‐L 2 Pt Corners and Four Butadiynediyl Linkers; Syntheses, Electronic Structures, and Square versus Skew Rhombus Geometries

   https://doi.org/10.1002/chem.202100305  

   Collins, Brenna K. ; Clough Mastry, Melissa ; Ehnbom, Andreas ; Bhuvanesh, Nattamai ; Hall, Michael B. ; Gladysz, John A. ( June 2021 , Chemistry – A European Journal)

   The dialkyl malonate derived 1,3‐diphosphines R₂C(CH₂PPh₂)₂(R=a, Me;b, Et;c,n‐Bu;d,n‐Dec;e, Bn;f,p‐tolCH₂) are combined with (p‐tol₃P)₂PtCl₂ortrans‐(p‐tol₃P)₂Pt((C≡C)₂H)₂to give the chelatescis‐(R₂C(CH₂PPh₂)₂)PtCl₂(2 a–f, 94–69 %) orcis‐(R₂C(CH₂PPh₂)₂)Pt((C≡C)₂H)₂(3 a–f, 97–54 %). Complexes3 a–dare also available from2 a–dand excess 1,3‐butadiyne in the presence of CuI (cat.) and excess HNEt₂(87–65 %). Under similar conditions,2and3react to give the title compounds [(R₂C(CH₂PPh₂)₂)[Pt(C≡C)₂]₄(4 a–f; 89–14 % (64 % avg)), from which ammonium salts such as the co‐product [H₂NEt₂]⁺Cl⁻are challenging to remove. Crystal structures of4 a,bshow skew rhombus as opposed to square Pt₄geometries. The NMR and IR properties of4 a–fare similar to those of mono‐ or diplatinum model compounds. However, cyclic voltammetry gives only irreversible oxidations. As compared to mono‐platinum or Pt(C≡C)₂Pt species, the UV‐visible spectra show much more intense and red‐shifted bands. Time dependent DFT calculations define the transitions and principal orbitals involved. Electrostatic potential surface maps reveal strongly negative Pt₄C₁₆cores that likely facilitate ammonium cation binding. Analogous electronic properties of Pt₃C₁₂and Pt₅C₂₀homologs and selected equilibria are explored computationally.

    

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4. 4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

   https://doi.org/10.3390/molecules25143189  

   Henke, Wade C. ; Hopkins, Julie A. ; Anderson, Micah L. ; Stiel, Jonah P. ; Day, Victor W. ; Blakemore, James D. ( July 2020 , Molecules)

   null (Ed.)

   4,5-diazafluorene (daf) and 9,9’-dimethyl-4,5-diazafluorene (Me2daf) are structurally similar to the important ligand 2,2’-bipyridine (bpy), but significantly less is known about the redox and spectroscopic properties of metal complexes containing Me2daf as a ligand than those containing bpy. New complexes Mn(CO)3Br(daf) (2), Mn(CO)3Br(Me2daf) (3), and [Ru(Me2daf)3](PF6)2 (5) have been prepared and fully characterized to understand the influence of the Me2daf framework on their chemical and electrochemical properties. Structural data for 2, 3, and 5 from single-crystal X-ray diffraction analysis reveal a distinctive widening of the daf and Me2daf chelate angles in comparison to the analogous Mn(CO)3(bpy)Br (1) and [Ru(bpy)3]2+ (4) complexes. Electronic absorption data for these complexes confirm the electronic similarity of daf, Me2daf, and bpy, as spectra are dominated in each case by metal-to-ligand charge transfer bands in the visible region. However, the electrochemical properties of 2, 3, and 5 reveal that the redox-active Me2daf framework in 3 and 5 undergoes reduction at a slightly more negative potential than that of bpy in 1 and 4. Taken together, the results indicate that Me2daf could be useful for preparation of a variety of new redox-active compounds, as it retains the useful redox-active nature of bpy but lacks the acidic, benzylic C–H bonds that can induce secondary reactivity in complexes bearing daf. 

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5. Computational Screening of Efficient Single‐Atom Catalysts Based on Graphitic Carbon Nitride (g‐C 3 N 4 ) for Nitrogen Electroreduction

   https://doi.org/10.1002/smtd.201800368  

   Chen, Zhe ; Zhao, Jingxiang ; Cabrera, Carlos R. ; Chen, Zhongfang ( December 2018 , Small Methods)

   The development of low‐cost and efficient electrocatalysts for nitrogen reduction reaction (NRR) at ambient conditions is crucial for NH₃synthesis and provides an alternative to the traditional Harber‐Bosch process. Herein, by means of density functional theory (DFT) computations, the catalytic performance of a series of single metal atoms supported on graphitic carbon nitride (g‐C₃N₄) for NRR is evaluated. Among all the candidates, the Gibbs free energy change of the potential‐determining step for five single‐atom catalysts (SACs), namely Ti, Co, Mo, W, and Pt atoms supported on g‐C₃N₄monolayer, is lower than that on the Ru(0001) stepped surface. In particular, the single tungsten (W) atom anchored on g‐C₃N₄(W@g‐C₃N₄) exhibits the highest catalytic activity toward NRR with a limiting potential of −0.35 V via associative enzymatic pathway, and can well suppress the competing hydrogen evolution reaction. The high NRR activity and selectivity of W@g‐C₃N₄are attributed to its inherent properties, such as significant positive charge and large spin moment on the W atom, excellent electrical conductivity, and moderate adsorption strength with NRR intermediates. This work opens up a new avenue of N₂reduction for renewable energy supplies and helps guide future development of single‐atom catalysts for NRR and other related electrochemical process.

    

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