Interpenetrated Metal-Porphyrinic Framework for Enhanced Nonlinear Optical Limiting

Structural interpenetration in metal-organic frameworks (MOFs) significantly impacts on their properties and functionalities. However, understanding the interpenetration on third-order nonlinear optics (NLO) of MOFs have not been reported to date. Herein, we report two 3D porphyrinic MOFs, a 2-fold interpenetrated [Zn₂(TPyP)(AC)₂] (ZnTPyP-1) and a noninterpenetrated [Zn₃(TPyP)(H₂O)₂(C₂O₄)₂] (ZnTPyP-2), constructed from 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP(H₂)) and Zn(NO₃)₂ (AC = acetate, C₂O₄ = oxalate). ZnTPyP-1 achieves excellent optical limiting (OL) performance with a giant nonlinear absorption coefficient (3.61 × 10⁶ cm/GW) and large third-order susceptibility (7.73 × 10⁻⁷ esu), which is much better than ZnTPyP-2 and other reported OL materials. The corresponding MOFs nanosheets are dispersed into a polydimethylsiloxane (PDMS) matrix to form highly transparent and flexible MOFs/PDMS glasses for practical OL application. In addition, the OL response optimized by adjusting the MOFs concentration in the PDMS matrix and the type of metalloporphyrin are discussed in the ZnTPyP-1 system. The theoretical calculation confirmed that the abundant π-π interaction from porphyrinic groups in the interpenetrated framework increased the electron delocalization/transfer and boosted the OL performance. This study opens a new avenue to enhance OL performance by the construction of interpenetrated structures and provides a new approach for the preparation of transparent and flexible MOF composites in nonlinear optical applications.