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Giant Enhancement of Second Harmonic Generation Accompanied by the Structural Transformation of 7-Fold to 8-Fold Interpenetrated Metal–Organic Frameworks (MOFs)
Authors:Zhihui Chen  Gianpiero Gallo  Dr Vaishali A Sawant  Dr Tianxiang Zhang  Dr Menglong Zhu  Dr Liangliang Liang  Dr Anjana Chanthapally  Dr Geetha Bolla  Hong Sheng Quah  Prof?Dr Xiaogang Liu  Prof?Dr Kian Ping Loh  Prof?Dr Robert E Dinnebier  Prof?Dr Qing-Hua Xu  Prof?Dr Jagadese J Vittal
Institution:1. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore;2. Max-Planck-Institute for Solid State Research, Heisenbergstrasse 1, Stuttgart, 70569 Germany

Department of Chemistry and Biology “A. Zambelli”, University of Salerno, Via Giovanni Paolo II, 132, Fisciano (SA), 84084 Italy;3. Max-Planck-Institute for Solid State Research, Heisenbergstrasse 1, Stuttgart, 70569 Germany

Abstract:Interpenetration in metal–organic frameworks (MOFs) is an intriguing phenomenon with significant impacts on their properties, and functional applications. Herein, we show that a 7-fold interpenetrated MOF ( 1 ) is transformed into an 8-fold interpenetrated MOF by the loss of DMF in a single-crystal-to-single-crystal manner. This is accompanied by a giant enhancement of the second harmonic generation (SHG ca. 125 times) and two-photon photoluminescence (ca. 14 times). The strengthened π–π interaction between the individual diamondoid networks and intensified oscillator strength of the molecules aid the augment of dipole moments and boost the nonlinear optical conversion efficiency. Large positive and negative thermal expansions of 1 occur at 30–150 °C before the loss of DMF. These results offer an avenue to manipulate the NLO properties of MOFs using interpenetration and provide access to tunable single-crystal NLO devices.
Keywords:Metall-organische Gerüste  Nichtlineare Optik  Frequenzverdopplung  Einkristall-Einkristall-Umwandlung
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