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1. Electron transport in a sequentially doped naphthalene diimide polymer

   https://doi.org/10.1039/d0ma00406e  

   Al Kurdi, Khaled; Gregory, Shawn A.; Jhulki, Samik; Conte, Maxwell; Barlow, Stephen; Yee, Shannon K.; Marder, Seth R. (September 2020, Materials Advances)

   null (Ed.)

   The effects of sequential n-doping on a high-electron-mobility naphthalene-diimide-based copolymer poly[( N , N ′-bis(2-decyltetradecyl)-naphthalene-1,8:4,5-bis(dicarboximide)-2,6-diyl)-(selenophene-2,5-diyl)-(benzo[ c ][1,2,5]thiadiazole-4,7-diyl)-(selenophene-2,5-diyl)], PNBS, are reported. Grazing-incidence XRD measurements show that PNBS doped with 2,2′-bis(4-(dimethylamino)phenyl)-1,1′,3,3′-tetramethyl-2,2′,3,3′-tetrahydro-1 H ,1′ H -2,2′-bibenzo[ d ]imidazole, (N-DMBI) 2 , has increased order relative to both the pristine polymer and a film doped with ruthenium pentamethylcyclopentadienyl mesitylene dimer. Films of PNBS optimally doped with (N-DMBI) 2 show electrical conductivities approaching 2 mS cm −1 in air. Temperature-dependent electrical measurements suggest that the polaronic charge carriers are highly localized, which is consistent with the moderate conductivity values obtained. 

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2. Cage Match: Comparing the Anion Binding Ability of Isostructural Versus Isofunctional Pairs of Metal‐Organic Nanocages

   https://doi.org/10.1002/chem.202303013  

   Dutton, Kaitlyn G; Jones, Taro J; Emge, Thomas J; Lipke, Mark C (January 2024, 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. 

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3. Fluoride Binding by a Neutral Organoantimony(V) Lewis Acid Embedded within a Dibenzodithiophene Chromophore

   https://doi.org/10.1002/zaac.202400170  

   Christianson, Anna M; Kim, Ahran; Murphy, Brendan L; Gabbaï, François P (February 2025, Zeitschrift für anorganische und allgemeine Chemie)

   Organoantimony Lewis acids have been coveted for their ability to bind hard anions like fluoride in competing media. Herein, we describe the synthesis of a phenyl dithienostibole (1) in which the antimony(III) center is embedded within a planar dibenzodithiophene chromophore. Compound1reacts witho‐chloranil to form the corresponding catecholatostiborane (2); it also reacts withtert‐butyl peroxide in the presence of perfluoropinacol to form the corresponding pinacolatostiborane (3). Compound2was investigated as a platform for anion binding. UV–vis titrations in CH₂Cl₂afforded an association constant greater than 10⁷ M⁻¹pointing to the high fluoridophilicity of this new system. Density functional theory calculations highlight the role played by theσ*(Sb‐C_phenyl) orbital in imparting Lewis acidity to the antimony center of2. 

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4. New Isoxazole‐Substituted Aryl Iodides: Metal‐Free Synthesis, Characterization and Catalytic Activity

   https://doi.org/10.1002/ejoc.202301191  

   Rimi; Uttam, Bhawna; Zhdankin, Viktor V.; Kumar, Ravi (February 2024, European Journal of Organic Chemistry)

   Abstract A series of new isoxazole‐substituted aryl iodides1 a–1 dhave been synthesized by DIB‐mediated [3+2] cycloaddition reaction of 2‐iodo‐1,3‐bis(prop‐2‐yn‐1‐yloxy) benzene (4) with corresponding benzaldehyde oximes5 a–5 d. Structure of the synthesized aryl iodides1were characterized by IR,¹H NMR,¹³C NMR and HRMS. The structure of1 awas also confirmed by single‐crystal X‐ray crystallography. Further, catalytic activity of iodoarenes1 a–1 dwas screened for the oxidation of hydroquinones and sulfides. On oxidation using aryl iodides1withm‐CPBA as terminal oxidant, hydroquinones afforded benzoquinones while sulfides gave corresponding sulfoxides in good to excellent yields. Iodoarene1 bshowed the best catalytic activity for the oxidation of sulfides and hydroquinones. Moreover, iodoarene1 b, was also utilized for α‐oxytosylation of acetophenones. 

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5. Computational exploration of the copper(I)‐catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives

   https://doi.org/10.1002/jcc.27433  

   Askerova, Ulviyya; Abdullayev, Yusif; Shikhaliyev, Namiq; Maharramov, Abel; Nenajdenko, Valentine G; Autschbach, Jochen (May 2024, Journal of Computational Chemistry)

   Abstract This computational study explores the copper (I) chloride catalyzed synthesis of (E)‐1‐(2,2‐dichloro‐1‐phenylvinyl)‐2‐phenyldiazene (2Cl‐VD) from readily available hydrazone derivative and carbon tetrachloride (CCl₄).2Cl‐VDhas been extensively utilized to synthesize variety of heterocyclic organic compounds in mild conditions. The present computational investigations primarily focus on understanding the role of copper (I) andN¹,N¹,N²,N²‐tetramethylethane‐1,2‐diamine (TMEDA) in this reaction, TMEDA often being considered a proton scavenger by experimentalists. Considering TMEDA as a ligand significantly alters the energy barrier. In fact, it is only 8.3 kcal/mol higher compared to the ligand‐free (LF) route for the removal of a chlorine atom to form the radical·CCl₃but the following steps are almost barrierless. This intermediate then participates in attacking the electrophilic carbon in the hydrazone. Crucially, the study reveals that the overall potential energy surface is thermodynamically favorable, and the theoretical turnover frequency (TOF) value is higher in the case of Cu(I)‐TMEDA complex catalyzed pathway. 

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