Quantifying Structural Polarization by Continuous Regulation of Lone-Pair Electron Expression in Molecular Crystals.
J Am Chem Soc
; 146(32): 22469-22475, 2024 Aug 14.
Article
in En
| MEDLINE
| ID: mdl-39090075
ABSTRACT
Rational design of structural polarization is vital for modern technologies, as it allows the physical properties of functional materials to be tailored. An effective approach for governing polarization involves the utilization of stereochemical lone-pair electrons (LPEs). However, despite the recognized significance of LPEs in controlling structural polarization, there remains a lack of understanding regarding the quantitative relationship between their expression and the extent of structural polarization. Here, by using pressure to continuously tune the LPE expression, we achieve the precise control and quantification of structural polarization, which brings enhanced second harmonic generation (SHG) of the molecular crystal SbI3·3S8. We introduce the I-Sb-I angle (αÌ
) that describes the degree of LPE expression and establishes a quantitative relationship between αÌ
and structural polarization. That is, decreasing αÌ
shapes LPE expression from delocalization to localization, which repels the bonding pairs of electrons and thus enhances the structural polarization. In addition, we extend this quantified relationship to a series of molecular crystals and demonstrate its applicability to the design of structural polarization by tailoring LPE expression.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Am Chem Soc
Year:
2024
Type:
Article
Affiliation country:
China