Building Fluorinated Hybrid Crystals: Understanding the Role of Noncovalent Interactions

Munárriz, J. (Universidad de Zaragoza) ; Rabuffetti, F.A. ; Contreras-García, J.

Resumen: Noncovalent interactions play a key role in functional materials. Metal-organofluorine interactions are of special interest because they directly affect the structure and reactivity of hybrid fluorinated materials. In-depth understanding and modulating of these interactions would enable the rational design of functional materials from fundamental chemical principles. In this work, we propose a computational approach that enables a comprehensive and quantitative characterization of noncovalent interactions (NCIs) in hybrid fluorinated crystals. Our approach couples dispersion-corrected density functional theory to NCI analysis. Additionally, we determine electron densities at bond critical points and identify electrostatic interactions using a simple electrostatic model. The versatility of this approach to probe a wide range of NCIs is demonstrated for a series of four bimetallic fluorinated crystals incorporating alkali-manganese(II) pairs and trifluoroacetato ligands. Noncovalent interactions in these hybrid crystals include metal-oxygen, metal-fluorine, hydrogen bonds, and van der Waals forces. Using K2Mn2(tfa)6(tfaH)2·H2O as an example, we demonstrate that its two-dimensional layered structure stems from a unique balance between these four NCIs. The computational approach presented herein should have general applicability to the quantitative study of NCIs in hybrid crystals, thereby serving as a guide for crystal engineering of novel hybrid materials.

Idioma: Inglés

DOI: 10.1021/acs.cgd.8b01105

Año: 2018

Publicado en: CRYSTAL GROWTH & DESIGN 18 (2018), 6901-6910
ISSN: 1528-7483

Factor impacto JCR: 4.153 (2018)

Categ. JCR: CRYSTALLOGRAPHY rank: 2 / 25 = 0.08 (2018) - Q1 - T1
Categ. JCR: MATERIALS SCIENCE, MULTIDISCIPLINARY rank: 66 / 293 = 0.225 (2018) - Q1 - T1
Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 47 / 172 = 0.273 (2018) - Q2 - T1

Factor impacto SCIMAGO: 1.046 - Chemistry (miscellaneous) (Q1) - Materials Science (miscellaneous) (Q1) - Condensed Matter Physics (Q1)

Financiación: info:eu-repo/grantAgreement/ES/MEC/EST16-00466
Financiación: info:eu-repo/grantAgreement/ES/MEC/FPU14-06003

Tipo y forma: Article (PostPrint)

Área (Departamento): Área Química Física (Dpto. Química Física)