Anion Recognition by Organometallic Calixarenes: Analysis from Relativistic DFT Calculations

Autor(es)

Ortolan, Alexandre O. ^[1] ; Oestrom, Ina ^[1] ; Caramori, Giovanni F. ^[1] ; Parreira, Renato L. T. ^[2] ; Munoz-Castro, Alvaro ^[3] ; Bickelhaupt, F. Matthias ^{[4, 5, 6]}

Afiliação do(s) autor(es)

^[1] Univ Fed Santa Catarina, Dept Quim, Campus Univ Trindade, CP 476, BR-88040900 Florianopolis, SC - Brazil

^[2] Univ Franca, Nucleo Pesquisas Ciencias Exatas & Tecnol, BR-14404600 Franca, SP - Brazil

^[3] Univ Autonoma Chile, Lab Quim Inorgan & Mat Mol, Llano Subercaceaux 2801, Santiago 8910060 - Chile

^[4] Vrije Univ Amsterdam, Dept Theoret Chem, De Boelelaan 1083, NL-1081 HV Amsterdam - Netherlands

^[5] Vrije Univ Amsterdam, ACMM, De Boelelaan 1083, NL-1081 HV Amsterdam - Netherlands

^[6] Radboud Univ Nijmegen, Inst Mol & Mat, Heyendaalseweg 135, NL-6525 AJ Nijmegen - Netherlands

• Tipo de documento: Artigo Científico
• Fonte: Organometallics; v. 37, n. 13, p. 2167-2176, JUL 9 2018.
• Citações Web of Science: 7

Resumo

The physical nature of the noncovalent interactions involved in anion recognition was investigated in the context of metalated calix{[}4]arene hosts, employing Kohn-Sham molecular orbital (KS-MO) theory, in conjunction with a canonical energy decomposition analysis, at the dispersion-corrected DFT level of theory. Computed data evidence that the most stable host-guest bonding occurs in ruthenium complexed hosts, followed by technetium and molybdenum metalated macrocyclic receptors. Furthermore, the guest's stenc fit in the host scaffold is a selective and crucial criterion to the anion recognition. Our analyses reveal that coordinated charged metals provide a larger electrostatic stabilization to amon recognition, shifting the calixarenes cavity toward an electron deficient acidic character. I his study contributes to the design and development or new organometallic macrocyclic hosts with increased anion recognition specificity. (AU)

• Processo FAPESP: 11/07623-8 - Utilização de métodos mecânicos-quânticos para estudo das ligações e interações químicas em sistemas auto-organizados com aplicação em catálise, química medicinal, eletrocromismo, armazenamento e conversão de energia
• Beneficiário: Renato Luis Tame Parreira
• Modalidade de apoio: Auxílio à Pesquisa - Jovens Pesquisadores