0000000000205636
AUTHOR
Lev N. Zakharov
Molecule Isomerism Modulates the Diradical Properties of Stable Singlet Diradicaloids
Inclusion of quinoidal cores in conjugated hydrocarbons is a common strategy to modulate the properties of diradicaloids formed by aromaticity recovery within the quinoidal unit. Here we describe an alternative approach of tuning of diradical properties in indenoindenodibenzothiophenes upon anti → syn isomerism of the benzothiophene motif. This alters the relationship of the S atom with the radical center from linear to cross conjugation yet retains the same 2,6-naphtho conjugation pattern of the rearomatized core. We conduct a full comparison between the anti and syn derivatives based on structural, spectroscopic, theoretical, and magnetic measurements, showing that these systems are stabl…
Diindeno-fusion of an anthracene as a design strategy for stable organic biradicals
The consequence of unpaired electrons in organic molecules has fascinated and confounded chemists for over a century. The study of open-shell molecules has been rekindled in recent years as new synthetic methods, improved spectroscopic techniques and powerful computational tools have been brought to bear on this field. Nonetheless, it is the intrinsic instability of the biradical species that limits the practicality of this research. Here we report the synthesis and characterization of a molecule based on the diindeno[b,i]anthracene framework that exhibits pronounced open-shell character yet possesses remarkable stability. The synthetic route is rapid, efficient and possible on the gram sca…
Exploration of the Solid-State Sorption Properties of Shape-Persistent Macrocyclic Nanocarbons as Bulk Materials and Small Aggregates.
Porous molecular materials combine benefits such as convenient processability and the possibility for atom-precise structural fine-tuning which makes them remarkable candidates for specialty applications in the areas of gas separation, catalysis, and sensing. In order to realize the full potential of these materials and guide future molecular design, knowledge of the transition from molecular properties into materials behavior is essential. In this work, the class of compounds termed cycloparaphenylenes (CPPs)-shape-persistent macrocycles with built-in cavities and radially oriented π-systems-was selected as a conceptually simple class of intrinsically porous nanocarbons to serve as a platf…
Diindenoanthracene Diradicaloids Enable Rational, Incremental Tuning of Their Singlet-Triplet Energy Gaps
Summary A fundamental understanding of the inherent electronic and magnetic properties of open-shell diradicaloids is essential so that these properties can be modified to create molecules that meet the potential needs of industry. However, there have been very few attempts to date to systematically accomplish this in diradicaloid compounds. Here, we present the synthetic, spectroscopic, and computational investigation of a series of molecules based on the diindeno[1,2-b:1′,2′-g]anthracene framework. Calculations suggest that by altering the transfer integral term, tab, we are able to manipulate the diradical character and, thus, ΔEST within this series of molecules. Experimentally determin…
A Tale of Two Isomers: Enhanced Antiaromaticity/Diradical Character versus Deleterious Ring‐Opening of Benzofuran‐fused s ‐Indacenes and Dicyclopenta[ b , g ]naphthalenes
We examine the effects of fusing two benzofurans to s-indacene (indacenodibenzofurans, IDBFs) and dicyclopenta[b,g]naphthalene (indenoindenodibenzofurans, IIDBFs) to control the strong antiaromaticity and diradical character of these core units. Synthesis via 3-functionalized benzofuran yields syn-IDBF and syn-IIDBF. syn-IDBF possesses a high degree of paratropicity, exceeding that of the parent hydrocarbon, which in turn results in strong diradical character for syn-IIDBF. In the case of the anti-isomers, synthesized via 2-substituted benzofurans, these effects are decreased; however, both derivatives undergo an unexpected ring-opening reaction during the final dearomatization step. All th…
Late-Stage Modification of Electronic Properties of Antiaromatic and Diradicaloid Indeno[1,2-b]fluorene Analogues via Sulfur Oxidation
The ability to alter optoelectronic and magnetic properties of molecules at a late stage in their preparation is in general a nontrivial feat. Here, we report the late-stage oxidation of benzothiop...
CCDC 1995028: Experimental Crystal Structure Determination
Related Article: Justin J. Dressler, Joshua E. Barker, Lucas J. Karas, Hannah E. Hashimoto, Ryohei Kishi, Lev N. Zakharov, Samantha N. MacMillan, Carlos J. Gomez-Garcia, Masayoshi Nakano, Judy I. Wu, Michael M. Haley|2020|J.Org.Chem.|85|10846|doi:10.1021/acs.joc.0c01387
CCDC 2077070: Experimental Crystal Structure Determination
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CCDC 1961176: Experimental Crystal Structure Determination
Related Article: Tobias A. Schaub, Ephraim A. Prantl, Julia Kohn, Markus Bursch, Checkers R. Marshall, Erik J. Leonhardt, Terri C. Lovell, Lev N. Zakharov, Carl K. Brozek, Siegfried R. Waldvogel, Stefan Grimme, Ramesh Jasti|2020|J.Am.Chem.Soc.|142|8763|doi:10.1021/jacs.0c01117
CCDC 1949614: Experimental Crystal Structure Determination
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CCDC 1949404: Experimental Crystal Structure Determination
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CCDC 1949613: Experimental Crystal Structure Determination
Related Article: Justin J. Dressler, Abel Cárdenas Valdivia, Ryohei Kishi, Gabriel E. Rudebusch, Austin M. Ventura, Brian E. Chastain, Carlos J. Gómez-García, Lev N. Zakharov, Masayoshi Nakano, Juan Casado, Michael M. Haley|2020|Cell Press: Chem|6|1353|doi:10.1016/j.chempr.2020.02.010
CCDC 1994473: Experimental Crystal Structure Determination
Related Article: Justin J. Dressler, Joshua E. Barker, Lucas J. Karas, Hannah E. Hashimoto, Ryohei Kishi, Lev N. Zakharov, Samantha N. MacMillan, Carlos J. Gomez-Garcia, Masayoshi Nakano, Judy I. Wu, Michael M. Haley|2020|J.Org.Chem.|85|10846|doi:10.1021/acs.joc.0c01387
CCDC 2077067: Experimental Crystal Structure Determination
Related Article: Joshua E. Barker, Tavis W. Price, Lucas J. Karas, Ryohei Kishi, Samantha N. MacMillan, Lev N. Zakharov, Carlos J. G��mez���Garc��a, Judy I. Wu, Masayoshi Nakano, Michael M. Haley|2021|Angew.Chem.,Int.Ed.|60|22385|doi:10.1002/anie.202107855
CCDC 1949611: Experimental Crystal Structure Determination
Related Article: Justin J. Dressler, Abel Cárdenas Valdivia, Ryohei Kishi, Gabriel E. Rudebusch, Austin M. Ventura, Brian E. Chastain, Carlos J. Gómez-García, Lev N. Zakharov, Masayoshi Nakano, Juan Casado, Michael M. Haley|2020|Cell Press: Chem|6|1353|doi:10.1016/j.chempr.2020.02.010
CCDC 1949612: Experimental Crystal Structure Determination
Related Article: Justin J. Dressler, Abel Cárdenas Valdivia, Ryohei Kishi, Gabriel E. Rudebusch, Austin M. Ventura, Brian E. Chastain, Carlos J. Gómez-García, Lev N. Zakharov, Masayoshi Nakano, Juan Casado, Michael M. Haley|2020|Cell Press: Chem|6|1353|doi:10.1016/j.chempr.2020.02.010
CCDC 2076414: Experimental Crystal Structure Determination
Related Article: Joshua E. Barker, Tavis W. Price, Lucas J. Karas, Ryohei Kishi, Samantha N. MacMillan, Lev N. Zakharov, Carlos J. G��mez���Garc��a, Judy I. Wu, Masayoshi Nakano, Michael M. Haley|2021|Angew.Chem.,Int.Ed.|60|22385|doi:10.1002/anie.202107855
CCDC 1589136: Experimental Crystal Structure Determination
Related Article: Joshua E. Barker, Justin J. Dressler, Abel Cárdenas Valdivia, Ryohei Kishi, Eric T. Strand, Lev N. Zakharov, Samantha N. MacMillan, Carlos J. Gómez-García, Masayoshi Nakano, Juan Casado, Michael M. Haley|2019|J.Am.Chem.Soc.|142|1548|doi:10.1021/jacs.9b11898
CCDC 1961177: Experimental Crystal Structure Determination
Related Article: Tobias A. Schaub, Ephraim A. Prantl, Julia Kohn, Markus Bursch, Checkers R. Marshall, Erik J. Leonhardt, Terri C. Lovell, Lev N. Zakharov, Carl K. Brozek, Siegfried R. Waldvogel, Stefan Grimme, Ramesh Jasti|2020|J.Am.Chem.Soc.|142|8763|doi:10.1021/jacs.0c01117
CCDC 1995029: Experimental Crystal Structure Determination
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CCDC 1964314: Experimental Crystal Structure Determination
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CCDC 2077069: Experimental Crystal Structure Determination
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CCDC 1961179: Experimental Crystal Structure Determination
Related Article: Tobias A. Schaub, Ephraim A. Prantl, Julia Kohn, Markus Bursch, Checkers R. Marshall, Erik J. Leonhardt, Terri C. Lovell, Lev N. Zakharov, Carl K. Brozek, Siegfried R. Waldvogel, Stefan Grimme, Ramesh Jasti|2020|J.Am.Chem.Soc.|142|8763|doi:10.1021/jacs.0c01117
CCDC 2077068: Experimental Crystal Structure Determination
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CCDC 1995030: Experimental Crystal Structure Determination
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CCDC 1426708: Experimental Crystal Structure Determination
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