2026-04-17T03:07:36Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/253072024-10-29T23:15:37Zcom_2072_452955com_2072_2054col_2072_453073

Computational Insights into the Regioselectivity of 1,3-Dipolar Cycloadditions inside Carbon Nanotubes Tomasini, Michele Marforio, Tainah Dorina Calveresi, Matteo Poater Teixidor, Albert Poater i Teixidor, Jordi Agencia Estatal de Investigación Reaccions d'addició Addition reactions Nanotubs de carboni Carbon nanotubes Hidrocarburs Hydrocarbons Fenils Phenyls Nature’s enzymes exhibit remarkable substrate specificity and catalytic efficiency by transforming substrates within confined active sites. To emulate this, various molecular containers, including zeolites, cyclodextrins, calix[n]arenes, cavitands, cucurbit[n]urils, metal-organic frameworks, covalent organic frameworks, and carbon nanotubes (CNTs), have been explored. Among these, CNTs are notable for their unique physical and chemical properties, enabling them to control reactions through spatial confinement. This study investigates the effect of CNT encapsulation on metal-free 1,3-dipolar Huisgen cycloaddition reactions between benzyl azide and substituted alkynes. Experimental results showed that CNTs significantly enhance the selectivity for the 1,4-triazole product. Computational studies using density functional theory further elucidate the impact of CNT confinement on reaction mechanisms and regioselectivity. The findings reveal that confinement within CNTs alters potential energy surfaces, favoring 1,4-triazole formation over 1,5-triazole, driven by steric and electronic factors. Additionally, comparative analyses highlight the influence of CNT diameter on activation energies and product stability, particularly with energy decomposition analysis and noncovalent interaction plots. This research underscores the potential of CNTs as nanoscale reactors for controlled synthesis, providing insights into the design of new catalytic systems and advancing the field of molecular encapsulation for selective organic transformations The authors thank the Spanish Ministerio de Ciencia e Innovación for projects PID2021-127423NB-I00 and PID2022-138861NB-I00 and the Generalitat de Catalunya for projects 2021SGR623 and 2021SGR442. A.P. is a Serra Húnter Fellow and ICREA Academia Prize winner (2019). We thank Barcelona Supercomputing Centre for computational facilities (QHS-2024-2-0018, QHS-2024-2-0028, and QHS-2024-2-0039) Open Access funding provided thanks to the CRUE-CSIC agreement with American Chemical Society (ACS) 2024-09-01 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion peer-reviewed http://hdl.handle.net/10256/25307 http://hdl.handle.net/10256/25307 eng info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.4c03830 info:eu-repo/semantics/altIdentifier/issn/1932-7447 info:eu-repo/semantics/altIdentifier/eissn/1932-7455 PID2021-127423NB-I00 PID2022-138861NB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127423NB-I00/ES/CATALISIS PREDICTIVA PARA CAMBIAR EL ODEN SECUENCIAL ENTRE EXPERIMENTOS I CALCULOS/ Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess application/pdf American Chemical Society (ACS) Journal of Physical Chemistry C, 2024, vol. 28, núm. 36, p. 14961-14971 Articles publicats (D-Q)