Interpenetrated Metal-Porphyrinic Framework for Enhanced Nonlinear Optical Limiting

Abstract

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.

Two-dimensional metal-organic frameworks: from synthesis to bioapplications

“…Moreover, the functionalization of MOFs would be easily obtained either by modification of the building blocks previously or post-modification of pre-synthesized MOFs. Owing to these outstanding features, MOFs have been widely applied in the field of gas storage [ 2 ] and separations [ 3 , 4 ], nonlinear optics [ 5 ], catalysis [ 6 , 7 ], and sensing [ 8 , 9 ].…”

Record Aluminum Molecular Rings for Optical Limiting and Nonlinear Optics

“…Hybrid materials possessing flexibility and possible synergic effects of diverse components are promising OL materials. As a result, aggregated crystalline materials like coordination polymers, metal–organic frameworks and metal complexes are among the materials that might become the next generation in the current field [12–16] . A noteworthy reason is that the variation of metal ions and ligands may offer more opportunities for fine‐tuning of the optical properties.…”

“…As a result, aggregated crystalline materials like coordination polymers, metalorganic frameworks and metal complexes are among the materials that might become the next generation in the current field. [12][13][14][15][16] A noteworthy reason is that the variation of metal ions and ligands may offer more opportunities for fine-tuning of the optical properties. Metal molecular rings of high nuclearity have long fascinated chemists due to their aesthetically pleasing structures and interesting properties.…”

Novel Third-Order Nonlinear Optical Materials with Craig-Möbius Aromaticity

“…20−28 Our group has studied the third-order NLO properties of a series of metal clusters, metal-oxo clusters, and metal−organic frameworks in experiments and theoretical calculations. 20,22,29−31 The results show that the electron delocalization can be enhanced by adjusting the metal cluster core structure, 30 by ligand type, 22 and by constructing interspersed framework structures, 29 resulting in a richer π−π interaction and effectively improving the thirdorder NLO response. Meanwhile, aromatic molecules have high delocalization and stability, but the interesting subject of Craig-Mobius aromatic complexes as excellent third-order NLO materials has been rarely addressed.…”

“…Third-order nonlinear optical (NLO) materials can be widely used for eye protection, optical switching, radiation detectors, and sensors due to their structural characteristics. − So far, a broad range of inorganic compounds, organic compounds, and hybrid materials have been studied with respect to third-order NLO. − Our group has studied the third-order NLO properties of a series of metal clusters, metal-oxo clusters, and metal–organic frameworks in experiments and theoretical calculations. ,,− The results show that the electron delocalization can be enhanced by adjusting the metal cluster core structure, by ligand type, and by constructing interspersed framework structures, resulting in a richer π–π interaction and effectively improving the third-order NLO response. Meanwhile, aromatic molecules have high delocalization and stability, but the interesting subject of Craig-Möbius aromatic complexes as excellent third-order NLO materials has been rarely addressed.…”