Azide-Alkyne Interactions: A Crucial Attractive Force for Their Preorganization for Topochemical Cycloaddition Reaction

被引:13
作者
Bhandary, Subhrajyoti [1 ]
Pathigoolla, Atchutarao [1 ]
Madhusudhanan, Mithun C. [1 ]
Sureshan, Kana M. [1 ]
机构
[1] Indian Inst Sci Educ & Res Thiruvananthapuram, Sch Chem, Thiruvananthapuram 695551, Kerala, India
关键词
alkyne interactions; atomic polarizability; azides; crystal engineering; topochemical reactions; topological analysis; TO-CRYSTAL SYNTHESIS; SOLID-STATE; NONCOVALENT INTERACTIONS; CHALCOGEN BONDS; MODEL ENERGIES; PNICOGEN BONDS; CRYSTALEXPLORER; FUNCTIONALS; HALOGEN; PROGRAM;
D O I
10.1002/chem.202200820
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A new class of attractive intermolecular interaction between azide and ethynyl structural entities in a wide range of molecular crystals is reported. This interaction was systematically evaluated by using 11 geometrically different structural motifs that are preorganized to direct a solid-state topochemical azide-alkyne cycloaddition (TAAC) reaction. The supramolecular features of the azide-alkyne interaction were mapped by various crystallographic and quantum chemical approaches. Topological analysis shows the noticeable participation of electron density in the azide center dot center dot center dot alkyne interactions. Interestingly, reorientation of the atomic polarizabilities in vicinal azide and alkyne groups upon interaction in crystals favors soft orbital-guided TAAC reactions. Moreover, various solid-state and gas-phase energy decomposition methods of individual azide center dot center dot center dot alkyne interactions summarize that the strength (varies from -5.7 to -30.1 kJ mol(-1)) is primarily guided by the dispersion forces with a influencing contribution from the electrostatics.
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页数:8
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