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1. Rare Guest-Induced Electrical Conductivity of Zn-Porphyrin Metallacage Inclusion Complexes Featuring π-Donor/Acceptor/Donor Stacks

   https://doi.org/10.1021/acsami.3c15959  

   Benavides, Paola A. ; Gordillo, Monica A. ; Thibodeaux, Evan ; Yadav, Ashok ; Johnson, Evan ; Sachdeva, Rakesh ; Saha, Sourav ( December 2023 , ACS Applied Materials & Interfaces)
2. Divergent stereochemical outcomes in the insertion of donor/donor carbenes into the C–H bonds of stereogenic centers

   https://doi.org/10.1039/d1sc04622e  

   Dishman, Sarah N. ; Laconsay, Croix J. ; Fettinger, James C. ; Tantillo, Dean J. ; Shaw, Jared T. ( January 2022 , Chemical Science)

   Intramolecular C–H insertions with donor/donor dirhodium carbenes provide a concise and highly stereoselective method to set two contiguous stereocenters in a single step. Herein, we report the insertion of donor/donor carbenes into stereogenic carbon centers allowing access to trisubstituted benzodihydrofurans in a single step. This study illuminates, for the first time, the stereochemical impact on the carbene center and delineates the structural factors that enable control over both stereogenic centers. Sterically bulky, highly activated C–H insertion centers exhibit high substrate control yielding a single diastereomer and a single enantiomer of product regardless of the catalyst used. Less bulky, less activated C–H insertion centers exhibit catalyst control over the diastereomeric ratio (dr), where a single enantiomer of each diastereomer is observed with high selectivity. A combination of experimental studies and DFT calculations was used to elucidate the origin of these results. First, hydride transfer from the stereogenic insertion site proceeds with high stereoselectivity to the carbene center, thus determining the absolute configuration of the product. Second, the short lived zwitterionic intermediate can diaster-eoselectively ring-close by a hitherto unreported S E 2 mechanism that is either controlled by the substrate or the catalyst. These results demonstrate that donor/donor carbenes undergo uniquely stereoselective reactions that originate from a stepwise reaction mechanism, in contrast to the analogous concerted reactions of carbenes with one or more electron-withdrawing groups attached. 

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3. Asymmetric Cyclopropanation with 4-Aryloxy-1-sulfonyl-1,2,3-triazoles: Expanding the Range of Rhodium-Stabilized Donor/Acceptor Carbenes to Systems with an Oxygen Donor Group

   https://doi.org/10.1021/acs.joc.2c00978  

   Kubiak, Robert W. ; Tracy, William F. ; Alford, Joshua S. ; Davies, Huw M. ( November 2022 , The Journal of Organic Chemistry)
4. Donor group influence on dye-sensitized solar cell device performances: Balancing dye loading and donor size

   https://doi.org/10.1016/j.dyepig.2020.109074  

   David Ndaleh, D.N. ; Nugegoda, Dinesh ; Watson, Jonathon ; Cheema, Hammad ; Delcamp, Jared H. ( March 2021 , Dyes and Pigments)

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5. Molecular tetrominoes: selective masking of the donor π-face to control the configuration of donor–acceptor complexes

   https://doi.org/10.1039/D1OB02293H  

   Sartucci, Jenna L. ; Maity, Arindam ; Mohanan, Manikandan ; Bertke, Jeffery ; Kertesz, Miklos ; Gavvalapalli, Nagarjuna ( January 2022 , Organic & Biomolecular Chemistry)

   Understanding the doping mechanism in organic semiconductors and generating molecular design rules to control the doping process are crucial for improving the performance of organic electronics. Even though controlling the location and orientation of the dopant along the semiconductor backbone is an important step in the doping mechanism, studies in this direction are scarce as it is a challenging task. To address this, herein, we incorporated π-face masked (strapped) units in 1,4-bis(phenylethynylene)benzene (donor) to control the acceptor (dopant) location along the trimer, donor–acceptor binding strength, and acceptor ionization. Two strapped trimers, PCP and CPC, are synthesized with control over the location of the strapped repeat unit in the trimer. The trimers are complexed with the 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) acceptor in solution. DFT calculations show that DDQ residing on the non-strapped repeat unit (the percentage of this configuration is at least ca. 73%) has the highest binding energy for both PCP and CPC. The percentage of dopant ionization is higher in the case of strapped trimers (PCP and CPC) compared to that of linear control trimers (PLP and LPL) and the completely non-strapped (PPP) trimer. The percentage of dopant ionization increased by 15 and 59% in the case of PCP and CPC respectively compared to that of PPP. 

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